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- WORKS OF 
J. BISHOP TINGLE, Ph.D., 


PUBLISHED BY 


JOHN WILEY & SONS. 





Determination of Radicles in Carbon Compounds. 
By Dr. H. Meyer, Imperial and Royal University, 
Prague. Authorized translation by J. Bishop Tin- 
gle, Ph.D., F.C.S. Second American Edition, 
including matter specially prepared by Dr. Meyer 
for this edition. 12mo, xii+162 pages, cloth, $1.00. 


Spectrum Analysis. 
By John Landauer, Member of the Imperial Ger- 
man Academy of :-aturalists. Authorized English 
Edition by J. Bishop Tingle. 8vo, x-+239 pages, 
44 figures, cloth, $3.00. 








DETERMINATION OF RADICLES 


IN 


CARBON COMPOUNDS. 


BY 


DR. MEYER, 


Docent and Adjunct of the 
Imperial and Royal German University, Prague. 


AUTHORIZED TRANSLATION 


BY 


J BISHOP TINGLE PreD. FCS. ; 


Professor of Chemistry at Illinois College, 
Jacksonville, /il. 


SECOND EDITION REWRITTEN. 
FIRST THOUSAND. 





NEW YORK: 

JOHN WILEY & SONS. 
Lonpon: CHAPMAN & HALL, Lrimirep. 
1903. 


BN. 


aN 


"J. BISHOP TIN 


y er e 








PREFACE 10: SECOND: EDITION: 


THE usefulness of this little book has been shown 
by the comparatively quick exhaustion of the first 
edition. The present issue has been thoroughly re- 
vised by Dr. Meyer and the writer, the whole work 
has been reset, and more than twenty per cent. of new 
matter added, including several figures. The addi- 
tions are generally distributed, but attention may be 
called to the new alternative processes for the determi- 
nation of alkyls and carbonyl. The methods which 
are given for the determination of the nitroso and 
methylene groups have been described since the 
publication of the former edition. For the selection 
of the additions Dr. Meyer and the writer are almost 
equally responsible. In deference to the wish of one 
or two reviewers the author and subject indices have 
been combined. It is hoped that this issue may prove 
to be even more useful than the former one; the writer 
will be grateful for any suggestions or corrections 
tending towards this end. Thanks are due to Prof. 
W. A. Noyes, of the Rose Polytechnic Institute, 
Ferre “Haute; “Ind. and:-to: Dr. A. Pingle; of the 
University of Toronto, Canada, for revising the proof- 
sheets. 

J. BisHop TINGLE. 


ILLINOIS COLLEGE, JACKSONVILLE, ILL., 


January, 1903. 
iii 


ing 
eee 


end 
aye 


ter 





fr 








AUTHOR’S. PREFACE, 





THIS English edition of my ‘‘ Anleitung zur quanti- 
tativen Bestimmung der organischen Atomgruppen”’ 
has been prepared by Dr. J. Bishop Tingle, to whom I 
am greatly indebted for the care he has bestowed on 
it. I have endeavored to bring it into conformity 
with the present state of the science by various cor- 
rections and additions. It has been further improved 
by certain changes in arrangement which Dr. Tingle 
has made, and he has also added various notes. The 
present edition is thus a decided advancement on the 
German one, and I trust that in its new form it may 
gain many new friends whilst retaining its old ones. 


Dr. HANS MEYER. 
PRAGUE, October 1899. 


TRANSLATOR'’'S. PREFACE TO THE 
FIRST EDITION. 





THE success of the German edition of Dr. Meyer’s 
book was only one of the reasons that led to the prep- 
aration of this translation. The quantitative side of 
organic chemistry, apart from elementary analysis, is 
almost always neglected in the ordinary courses of in- 
struction, and when the need for it arises, in the pros- 
ecution of research work for instance, it is difficult to 
obtain a comprehensive view of the methods which are 
available without undue expenditure of time. This 
little work supplies, for the first time, a systematic | 
treatment of these methods which, it is hoped, may 
help to remove this drawback and may also encour- 
age the introduction of some quantitative work into 
the college courses of organic preparations, since such 
a departure could scarcely fail to be beneficial in 
various ways to the student. From the translator's 
experience with the German edition he believes that 
the present one will be serviceable to instructors and 
senior students of organic chemistry. Considerable 
care has been bestowed on the proof-sheets, and it is 
hoped that the errors which may have escaped notice 
are not too glaring. 

LEwWIs INSTITUTE, CHICAGO, ILL., 


October 1899. 
vi 


CONTENTS. 


ENTRODUCTOR Yo ic Oo rk no oe ee Oa Ore eS wie ene 
CHAPTER: i. 


I 
DETERMINATION GFL YDROXVE “OM oor oe a a ecee eis oe 
Determination of hydroxyl, 4. Acylation, 4 Prep- 
aration of acetyl derivatives, 6. (A) By acetyl chlo- 
ride, 6. (B) By acetyl bromide, 8. (C) By acetic anhy- 
dride, 8. (D) By glacial acetic acid, 10. (E) By chlor- 
acetyl chloride, 10. Isolation of acetyl derivatives, ro. 
Determination of the acetyl groups, 11. (A) Hydro- 
lytic methods, 11. (B) Additive method, 18. (C) 
Potassium acetate method, 18. (D) Distillation 
method, 19. Benzoyl derivatives, 21. (A) Preparation 
from benzoyl chloride, 21. (B) Preparation from 
benzoic anhydride, 25. (C) Preparation of substituted 
benzoic acid derivatives and of phenylsulphonic chlo- 
ride, 26. Acylation by means of substituted benzoic 
acid derivatives and of phenylsulphonic chloride, 27. 
Analysis of benzoyl derivatives, 28. Acylation by 
means of other acid radicles, 30. Alkylation of hy- 
droxyl groups, 31. Preparation of benzyl derivatives, 
32. Esterification of phenols, 33. Preparation of 
carbamates by means of carbamyl chloride, 33. Prep- 
aration of diphenylcarbamyl chloride, 34. Prepara- 
tion of phenylcarbamic acid derivatives, 35. Prepara- 
vii 


Vili CONTENTS. 
: PAGE 
tion of phenylisocyanate, 35. Action of phenylisocya- 
nate on hydroxyl derivatives, 35. Action of organic 
magnesium derivatives on hydroxyl compounds, 37. 


‘CHAPTER II. 


ee I 
DETERMINATION OF METHOXYL, CH;0-, ErHoxyt, C,H,Q-. 


AND CARBOXYL, CO.OH Ree eh Vou a SW 38 

Determination of methoxyl, S. Zeisel’s method, 38 
For non-volatile substances, 42. For volatile com- 
pounds, 45. Modified method, 46. Method for the 
differentiation of methoxyl and ethoxyl, 47. Deter- 
mination of ethoxyl, 48. -Determination of carboxy], 
48. (A) Analysis of metallic salts, 49. (B) Titration 
of acids, 50. (C) Etherification, 51. (D) Electrolytic 
conductivity of sodium salts, 53. (E) Indirect methods 
for the determination of the basicity of acids, 58. (i) 
Carbonate method, 58. (ii) Ammonia method, 59. 
(iii) Hydrogen sulphide method, 60. (a) Volumetric 
method, 61. (b) Titration method, 63. (iv) Iodine- 
oxygen method, 64. 


CHAPTER III. 


DETERMINATION OF CARBONYL, Co, METHYLENE, CH). Sian Oe 

Preparation of phenylhydrazones, 68. Preparation 
of parabromophenylhydrazine, 72. Substituted hy- 
drazones, 73. Indirect method, 74. Preparation of 
oximes, 80. Preparation of semicarbazones, 84, 87. 
Preparation of semicarbazine salts, 84. Preparation 
of thiosemicarbazine derivatives, 88. Preparation of 
semioxamazine, 90. Preparation of amidoguanidine 
derivatives, 90. Paramidodimethylaniline derivatives, 
92. Barium salts of aromatic aminocarboxylic and 
aminosulphonic acids, 93. Other derivatives of alde- 
hydes and ketones, 93. Determination of methylene, 


94. 


CON TENTS. 


CHAPTER IV. 


Determination of the amino group, 95. Determina- 
tion of aliphatic amines, (i) nitrous acid method, 95. 
(ii) Analysis of salts and double salts,97. (iii) Acety- 
lation, 97. (iv) Titration with cenanthaldehyde, 97 
Determination of aromatic amines, 97. (i) Titration of 
the salts, 98. (ii) Preparation of diazo-derivatives: (a) 
conversion into an azo dye, 99. (b) Indirect method, 
tor. (c) Azoimide method, 102. (d) Sandmeyer- 
Gattermann’s reaction, 103. (iii) Analysis of salts and 
double salts, 105. (iv) Acetylation, 106. Alkylation, 
108. Determination of the nitrile group, 108. De- 
termination of the amido group, 110. Determination 
of the imide group: (i) Acetvlation, 112. (ii) Alkyla- 
tion, 113. (iii) Analysis of salts, 113. (iv) Elimina- 
tion of imidogen as ammonia, 113. Determination of 
methyl imide, 114. (i) Determination with one alkyl 
linked to nitrogen, 114. (ii) Determination with two 
or more alkyls linked to nitrogen, 116. (iii) Successive 
determination of alkyl groups, 117. (iv) Determina- 
tion of methyl imide in presence of methoxyl, 117. (v) 
General remarks on the method, 118. Determination 
ef ethyl imide, 119. Differentiation of the methyl 
imide and ethyl imide groups, 119. 


CHAPTER V. 


Determination of the diazo-group (A) Aliphatic 
diazo-compounds: (i) Titration with iodine, 120. (ii) 
Analysis of the iodine derivative, 121. (iii) Determina- 
tion of the nitrogen in the wet way, 121. (B) Aromatic 
diazo-compounds. Diazonium derivatives, 123. De- 
termination of the hydrazide group, 125. (i) By 
oxidation, 125. (ii) Iodometric method, 127. Deter- 
mination of the nitro-group. (A) Titration method, 
129. (i) Method for non-volatile compounds, 130. (ii) 
Modifications for volatile compounds, 131. (B) Diazo- 


PAGE 


CONTENTS. 


PAGE 
method, 132. Determination of the nitroso-group, 1 42. 


Determination of the iodoso- and iodoxy-groups, 134. 
Determination of the peroxide group, 135. The iodine 
number, 136. Appendix, 141. Table of the weights 
of a cubic centimeter of hydrogen, 142. Tension of 





a 
aqueous vapor, 144. Table for the value of eemooagars 
144. Index, 147. 


ABBREVIATIONS. 


Tue following abbreviations have been used in the 
bibliographical references: 


Am. Chem. Journ. 


Ann. 

Ann. de Ch. Ph. 
Arch. Pharm. 
B. 


Bull. 

Cs 
Chak: 
Ch. Ztg. 
ChoN: 
cr, 


Ding]. 
Gazz. 
As i 


A 
de So 


Journ. Chem. Soc. 


cpr: 
M. 
Mc I. 


American Chemical Journal. 

Liebig’s Annalen der Chemie und Pharmacie. 

Annales de Chimie et de Physique. 

Archiv der Pharmacie. 

Berichte der Deutschen chemischen Gesell- 
schaft. 

Bulletins de la Société Chimique de Paris. 

Chemisches Centralblatt. 

Chemische Revue. 

Chemiker-Zeitung. 

Chemical News. 

Comptes rendus de 1’Académie des sciences 
(Paris). 

Dingler’s polytechnisches Journal. 

Gazzetta chimica italiana. 

Beilstein, Handbuch. 

Jahresbericht tiber die fortschritte der 
Chemie. 

Journal of the American Chemical Society. 

Journal of the Chemical Society of London. 

Journal fur praktische Chemie. 

Monatshefte fur Chemie. 

V. Meyer and P. Jacobson, ‘‘ Lehrbuch der 
organischen Chemie.” 

xi 


An. 

. anal. 

. ang. Ch. 
2 £. Oh: 


. Rub. 


. physiol. Ch. 


ABBREVIATIONS. 


Recueil des travaux chimiques des Pays- 
Bas. 

Seelig, ‘Organische Reaktionen und Re- 
agentien.” 

Wiedemann’s Annalen der Physik und 
Chemie. 

Zeitschrift fir physikalische Chemie. 

Zeitschrift fur anorganische Chemie. 

Zeitschrift fur analytische Chemie. 

Zeitschrift fir angewandte Chemie. 

Zeitschrift fur Chemie. 

Zeitschrift fur physiologische Chemie. 

Zeitschrift des Vereines fir Rubenzucker- 
industrie. 





pane 
OF 4 
CALIFORN 


——— 


DETERMINATION OF RADICLES IN 
CARBON COMPOUNDS. 


INTRODUCTION. 


THE quantitative analysis of inorganic compounds, 
as usually performed, consists almost exclusively in 
the determination of ions, as this generally suffices for 
the identification of the substance; but to attain the 
same end in the case of organic bodies the elementary 
analysis requires supplementing by other methods. 
The percentage composition gives no information about 
the relative arrangement of the atoms in the molecule, 
but the demand for methods of analysis which will 
yield such knowledge increases with our growing in- 
sight into the constitution of carbon compounds. To 
supply this want certain ‘‘ quantitative reactions ’’ have 
been applied for the determination of special groups of 
atoms; they are widely, but almost exclusively, em- 
ployed by technologists in the analysis of such sub- 
stances as fats, waxes, resins, ethereal oils, caoutchouc, 
glue, paper, etc., and the results are known as the 
‘‘acid number,’’ ‘‘saponification number,’’ ‘‘ iodine 
number,’’ ‘‘methoxyl number,’’ ‘‘ acetyl number,”’ 
‘carbonyl number,’’ etc. The determination of such 


’ 


2 RADICLES IN CARBON COMPOUNDS. 


‘“numbers’’ or ‘‘values’’ obtained by the action of 
some reagent on a known weight of substance is fre- 
quently insufficient for scientific investigation; this ren- 
ders it necessary to work out a special process for each 
group of organic compounds in order to determine the 
radicles which are present. 

The reactions of organic compounds are only in part 
ionic; usually they are conditioned by the configura- 
tion and state of equilibrium of the molecule, and con- 
sequently a reaction which readily occurs with one 
compound may totally fail with another of very similar 
constitution on account of stereoisomerism; or, by 
substitution, one radicle may approximate more or 
less closely to the character and functions of another 
In these cases the quantitative separation of the com- 
pounds is more difficult, and can frequently be accom- 
plished only by differences in crystallizing power, or 
by the preparation of derivatives which can be volatil- 
ized without decomposition. 

Since the course of a particular reaction of an inor- 
ganic compound is only conditioned by the behavior 
of the ions which are to be determined, it follows that 
the analytical methods are in a sense independent of 
the nature of the compounds investigated, and conse- | 
quently of very wide application. The matter is far 
otherwise with organic compounds: there are very few 
processes which, like Ziesel’s method for determining 
methoxyl, can be applied almost universally. Usually, 
then, it becomes necessary for the analyst himself to 
select the method most appropriate for his special pur- 
pose, or, perhaps by a combination of several, to de- 
vise one which may lead to the desired result. The 


INTRODUCTION. e 


successful methods hitherto proposed for the determina- 
tion of organic radicles have been collected together in 
this work, and it is hoped that they may serve to indi- 
cate the direction in which research may be success- 
fully prosecuted for the discovery of new ones applicable 
to hitherto unforeseen conditions. 


CHAPTER I. 
3 
DETERMINATION OF HYDROXYL (-OH). 


THE determination of the hydroxy] radicle in organic 
compounds depends on the preparation of derivatives by 
the following methods: 

(I.) ACYLATION.—This consists in the introduction 
into the hydroxyl compound of the radicle of one of 
the acids mentioned below: 

Acetic acid ; 

Benzotc acid and its substitution products; 

Phenylsulphonic acid. 

Of less frequent employment are the radicles of 

Propionic acid; 

Tsobutyric acid; 

Phenylacetic acid. 

(II.) ALKYLATION.—Confined usually to the prep- 
aration of dexzyl derivatives. 

(III.) The preparation: of CARBAMATES. 

(IV.) The formation of ESTERS OF PHENYLCARBAMIC 
ACID. : 

As a rule, attention is first directed to the prepara- 
tion of an acetyl or benzoyl derivative, the former 
usually by Liebermann & Hérmann’s method (see page 
8), the latter by that of Lossen or Schotten-Baumann 
(see page 22). Notinfrequently, however, it becomes 

4 


DETERMINATION OF HYDROXYL. 5 


necessary to resort to one of the other forms of pro- 
ceduré in order to determine the constitution of the 
body under investigation. As the groups NH, NH, 
and SH are all capable of acylation, care is required to 
avoid confusion, if the original compound contains nitro- 
gen or sulphur. Instances are known of acetylation 
taking place in the absence of hydroxyl and of the 
‘groups just referred to, thus diacetylhydroquinol is 
formed from quinone, acetic anhydride, and sodium 
acetate ;! tetrachloroquinone and acetyl chloride yield 
diacetyltetrachlorohydroquinol.? Acetylating reagents 
frequently cause isomerization or polymerization, and 
sometimes lead to the production of anhydrides, etc. ; 
thus benzhydrylacetocarboxylic anhydride is obtained 
from the isomeric orthocinnamocarboxylic acid by the 
action of acetic anhydride and sodium acetate,* and 
isocantharidin is produced from cantharic acid when 
heated ina sealed tube with acetyl chloride.‘ In view 
of these and similar facts, care should be taken to 
hydrolyse the presumptive acetyl derivative and identify 
the product with the original substance; should this 
not be possible, then proof must be obtained that the 
derivative does actually contain the acid radicle, the 
introduction of which has been attempted. 





1 Sarauw, B. 12, 680. 

2 Graehe, Ann. 146, 13. 

3 Benedikt and Ehrlich, M. 9, 529. 

4 Anderlini and Ghiro, B. 24, 1998. Cfs Pinner B. 27 (1894), 2861; 
28 (1895), 456. - 


6 RADICLES IN CARBON COMPOUNDS. 


METHODS OF ACETYLATION. 
(1) PREPARATION OF ACETYL DERIVATIVES. 


The following reagents are employed for the prepara- 
tion of acetyl derivatives from organic compounds con- 
taining hydroxyl groups: 

(A) Acetyl chloride; 

(B) Acetyl bromide, 

(C) Acetic anhydride, sodium acetate, 

(D) Glactal acetic acid; 

(E) Chloracetyl chloride. 


(A) Acetylation by Means of Acetyl Chloride. 


(2) Many hydroxyl derivatives react with acetyl 
chloride when simply mixed or digested on the water- 
bath. It is convenient to dissolve the substance and © 
the chloride in benzene, and boil the solution until the 
evolution of hydrochloric acid ceases. If there is no 
danger of the hydrogen chloride causing secondary 
reactions (hydrolysis), of which an interesting case has 
been recorded,! the substance may be heated with the 
chloride in a sealed tube without solvent. Certain 
dibasic hydroxy acids of the aliphatic series, such as 
mucic acid, which are not changed with acetyl chloride 
alone, frequently react with it on the addition of zinc 
chloride. In general, it may be stated that acetyl 
chloride only reacts readily with alcohols and phenols, 
but, as it may lead to the production of anhydrides 





1 Herzig and Schiff, B. 30, 397. Cf. Bamberger and Landsiedl, M. 
18, 307. Brauchbar and Kohn, /é7d. 19, 27, foot-note. 
2S., p. 258. 


DETERMINATION OF HYDROXYL. 7 


from polybasic acids, these are usually employed in 
the form of esters, the use of which has the additional 
advantage of yielding products that are much more 
easily distilled than the corresponding derivatives of 
the acids themselves.’ 

(4) The following method? is frequently more con- 
venient than the ‘‘acid’’ acetylation just described. 
The substance is dissolved in ether or benzene, and 
digested with the necessary quantity of acetyl chloride 
and dry alkali carbonate, the latter being in the pro- 
portion necessary to form a hydrogen salt as repre- 
sented by the equation: 


R.OH + CH,.COCI + K,CO, > R.O.CO.CH, + 
KCI KHCO:, 


(c) Acetylation by means of acetyl chloride and 
aqueous alkali is described on p. 24. 

(2) Itis often convenient to allow the acetyl chloride 
to react with the compound under investigation in 
pyridine solution.* 

(ec) Diacetylacetone could only be acetylated by 
allowing its barium salt to react with acetyl chloride 
at the ordinary temperature.‘ 

(7) Instead of acetyl chloride, phosphorus trichloride, 
or preferably the oxychloride, or phosgene may be 
employed; they are allowed to react on a mixture of 
the substance and acetic acid in the proper propor- 





1 Wislicenus, Ann. 129, 17. 

2 L. Claisen, B. 27, 3182. 

3 A. Deninger, B. 28, 1322. Cf. A. Einhorn and F. Hollandt, Ann. 
301 (1898). 95. 

* Feist, /éid. 28, 1824. 


8 RADICLES IN CARBON COMPOUNDS. 


tions.’ Thus, forexample, phenol is readily acetylated 
by heating it at 80° with an equimolecular proportion 
of acetic acid and adding phosphorus oxychloride 
(4 molecule) gradually, by means of a dropping funnel. 
When hydrogen chloride is no longer evolved the 
product is poured into cold aqueous soda solution; after 
further washing with highly dilute alkali it is treated 
once with water, dried by means of calcium chloride, 
and distilled. 


(B) Acetylation by Means of Acetyl Bromide. 


Acetyl bromide has been used? for the acetylation 
of certain sugars; the products are aceto bromides and 
usually crystallize well. | 


(C) Acetylation by Means of Acetic Anhydride. 


(2) The substance is generally boiled with 5—10 parts 
of anhydride, or heated with it in a sealed tube for 
several hours. The higher fatty acids yield anhydrides 
by this treatment.? 

(6) Not infrequently the substances must be allowed 
to react during a short time only, at a comparatively 
low temperature. Bebirine, for instance, is readily 
acetylated when digested with the anhydride during a 
short time at 40°-50°, but by its prolonged action 
amorphous substances are formed. 

(c) The substance may be mixed with an equal 
weight of dry sodium acetate, and 3-4 parts of the 





1J. pr. 25, 282; 26, 62; 31, 467. 

2W. Koenigs and E. Knorr, B. 34 (1901), 957; E. Fischer and E. F. 
Armstrong, /é7d. 2885. 

3 A. Albitzky, Journ. Chem. Soc. (1899) i, 862. J. Russ. Chem. Soc., 
31 (1899), 103. * B. 29, 2057. 


: DETERMINATION OF HYDROXYL. 9 


anhydride, and boiled for a short time in a reflux ap- 
paratus;! in the case of small quantities of substance 
2~3 minutes’ boiling may suffice. The action appears 
to depend on the production of a sodium salt of the 
compound under examination, which then reacts with 
the anhydride. This method yields, on the whole, 
the most trustworthy results of any, and seldom fails 
to give completely acetylated derivatives. It fails in 
the case of the a-hydroxyl] of the hydroxyquinolines,’ 
though these compounds yield benzoyl derivatives. 
Occasionally the presence of.sodium acetate is harmful.® 

(7) A mixture of acetic anhydride and acetyl chlo- 
ride may be used, or the action of the anhydride may 
be started by means of a drop of concentrated sulphuric 
acid, which frequently causes a vigorous reaction at 
the ordinary temperature when otherwise a high tem- 
perature and pressure would have to be employed. 
The method is applicable to many aldehydes, hydroxy- 
aldehydes, phenols, substituted phenols containing 
negative groups, and polyhydric alcohols, also to 
aminophenols and amines containing one or more nega- 
tive groups. It is less satisfactory with the ethers of 
phenols, and with hydrocarbons of the series C,H,,_,.° 

(e) The addition of zinc chloride* and of stannic 
chloride? has also been recommended. 








1.C, Liebermann and O. Hérmann, B. 11, 1619. 

2 J. Diamant, M. 16, 770. Cf. La Coste and Valeur, B. 20, 1822. 

3 Herzig, M. 18, 709. ‘ 

4 Franchimont, B. 12, 1941. Cf. Thiele, B. 31, 1249. 

5 G. Freyss, Journ. Chem. Soc., 76 (1899), i. 874. 

6. Franchimont, C. r. 89, 711; B. 12, 2058. Cf. Maquenne, Bull. 48, 
54, 7109- 

7H. A. Michael, B. 27, 2686. 


10 RADICLES IN CARBON COMPOUNDS. 


(7) Acetic anhydride in aqueous solution has also 
been successfully employed (cf. p. 7). 


(D) Acetylation by Means of Glacial Acetic Acid. 


Acetylation, especially that of alcoholic hydroxyl 
groups, may often be accomplished by heating the 
substance with glacial acetic acid, under pressure if 
necessary; the addition of sodium acetate is also ad- 
vantageous, and, in some cases, this is the only method 
which gives the desired result. Thus, camphorpinacone 
yields a chloride when treated with acetyl chloride, 
and is not changed by boiling acetic anhydride, but 
when it is boiled with glacial acetic acid for a short 
time, a stable acetyl derivative is formed, and an 
isomeric ‘‘ labile ’’ one by the action of the acid at the 
ordinary temperature during twenty-four hours.! 


(E) Acetylation by Means of Chloracetyl Chloride. 

This reagent has also been employed occasionally.? 

A collection has been made of references in the lit- 
erature to hydroxyl derivatives which are not capable 
of acetylation. 


ISOLATION OF THE ACETYL 
DERIVATIVES. 


Acetyl derivatives are isolated by pouring the pro- 
duct of the reaction into water. The excess of acetic 
acid may also be removed by the addition of methylic 
alcohol to convert it into methylic acetate, which is 





—__—_—_ 


1 Beckmann, Ann. 292, 17. 
2 Klobukowsky, B. ro, 881. Cf. /b¢d. 31, 2790; 20, 2330. 
3M. 19. 22. 


DETERMINATION OF HYDROXYL. II 


then volatilized; residual acetic anhydride is separated 
by distillation under reduced pressure. Acetyl deriva- 
tives, soluble in water, may often be precipitated by 
the addition of solid sodium carbonate, or by extract- 
ing the solution with chloroform or benzene. Ethylic 
acetate frequently proves to be an excellent medium 
for the subsequent recrystallization of the acetyl product. 


DETERMINATION OF THE ACETYL 
GROUPS. 


The various acetyl derivatives of a compound usually 
differ little in percentage composition, so that ele- 
mentary analysis seldom affords information as to the 
number of acetyl groups which have entered the orig- 
inal molecule; thus, the mono-, di-, and tri-acetyl de- 
rivatives of the trihydroxybenzenes have an identical 
percentage composition. In such cases the acetyl 
groups must be eliminated, and the acetic acid formed 
determined directly or indirectly. 


(A) Hydrolytic Methods. 


The following reagents are employed for the 
hydrolysis of acetyl compounds: 

(a) Water; 

(6) Potassium hydroxtde, sodium hydroxide; 

(c) Barium hydroxide; 

(a) Ammonia; 

(e) Chalk; 

(f) Magnesia; 

(¢) Hydrochloric acid; 

(hk) Sulphurtc acid; 

(2) Hydriodte acid. 


12 RADICLES IN CARBON COMPOUNDS. 


(a) Some acetyl derivatives are hydrolysed by heat- 
ing with water under pressure; thus butenyltriacetin, 
C,H, (C,H,O,),, is completely hydrolysed by heating 
it with forty parts of water at 160° in ‘a sealed tube, 
and the liberated acetic acid may be titrated.} 
Diacetylmorphine also loses one acetyl group by boil- 
ing it with water,? and acetyl dihydroxypyridine is still 
more unstable.® 

(6) Hydrolysis by means of potassium hydroxide or 
sodium hydroxide is especially useful for the analysis 
of fats. The compound (1-2 grams) is gently boiled 
on the water-bath for fifteen minutes, in a wide-necked 
flask of 100-150 cc. capacity, with alcoholic potash 
(25-50 cc.) of known strength, which should be about 
N/2. During the heating the neck of the flask is 
covered with a cold funnel; at the conclusion of the 
hydrolysis phenolphthalein is added, and the excess 
of alkali determined by means of N/2 hydrochloric 
acid. In some cases it is necessary to distill off the 
acetic acid before titration on account of the pro- 
duction of anhydrides of the higher fatty acids by 
the action on them of acetic anhydride. The method 
may also be employed for the determination of the 
molecular weight of the aliphatic alcohols. This is 


6100 
obtained from the expression M = ee — 42, where 





1 Lieben and Zeisel, M. 1, 835. 

* Wright- Becket, Journ. Ch, Soc., 12, 1033. Danckwortt, Arch. Pharm, 
226, 57- 

3M. 18, 619. 

4 Benedikt and Ulzer, M. 8, 41. | 

5 A. Albitzky, Journ. Chem, Soc. 76 (1899), i. 862. J. Russ. Chem. 
Soc. (1899), 31, 103. 


DETERMINATION OF HYDROXYL. 13 


M is the molecular weight, and V the number of milli- 
grams of potassium hydroxide required to hydrolyse | 
gram of the acetyl derivative. If the compound is 
affected by air, the hydrolysis is carried out in an at- 
mosphere of hydrogen;! should the original compound 
be insoluble in dilute hydrochloric acid, the acetyl de-. 
_ rivative may be boiled with aqueous potash, the pro- 
duct acidified, and the precipitate weighed.’ 


N 
Methyl alcoholic sodium hydroxide 3 has been suc- 


cessfully employed for the hydrolysis of octacetyl- 
sucrose. The mixture is allowed to remain at the 
_ ordinary temperature over night, and then titrated with 


RS 


re sulphuric acid, with phenolphthalein as indicator. 


(c) Barium hydroxide may be employed in many 
cases where potash causes decomposition, thus 
hematoxylin yields formic acid when boiled with 
highly dilute alkali, but barium hydroxide readily 
hydrolyses its acetyl derivatives without further de- 
composition.‘ One method of procedure ° is to boil the 
compound under investigation with the hydroxide dur- 
ing 5-6 hours in a reflux apparatus. The product is 
filtered, the filtrate treated with carbonic anhydride in 
excess, again filtered, and the filtrate evaporated. 
The residue is dissolved in water, the liquid filtered 





1 Klobukowsky, B. 10, 882. 

2 Vortmann, ‘‘ Anleitung zur chemischen Analyse organischer Stoffe,” 
P- 59- 

3 W. KGnigs and E. Knorr. B. 34 (1901), 4348. 

4 Erdmann and Schultz, Ann. 216, 234. 

5 Herzig, M. 5, 86. 


14 RADICLES IN CARBON COMPOUNDS. 


and, after being washed, the barium in the filtrate is 
determined as sulphate. Since all the above opera- 
tions are conducted in glass vessels and some alkali 
from these may neutralize a portion of the acetic acid, 
a correction becomes necessary. This is obtained by 
concentrating the filtrate from the barium sulphate in a 
platinum dish; when the excess of sulphuric acid has 
been volatilized, the residue is treated with pure am- 
monium carbonate until its weight becomes constant. 
It is now dissolved in water, the silica removed, and 
the sulphates in the filtrate determined as barium sul- 
phate, the weight of which is added to that first found. 
If the hydrolysis, etc., can be carried out in vessels of 
silver,! the above correction is unnecessary. The 
action of the barium hydroxide solution is promoted 
by the previous addition to the substance of a few 
drops of alcohol.’ 

(2) Aqueous ammonia readily hydrolyses the dia- 
cetyl derivative of benzoin yellow, alkalis cause de- 
composition.® 

(e) Chalk in aqueous suspension readily eliminates 
bromine and the acetyl group from acetyloxyacetophe- 
none bromide.‘ 

(7) Magnesia is generally employed in the following 
manner:> Ordinary ‘‘ignited magnesia,’’ and the 
basic carbonate (magnesia alba) are both unsuitable, 
as they contain alkali carbonates which are difficult to 





1 Lieben and Zeisel, M. 4, 42; 7, 69. 

2 Barth and Goldschmiedt, B. 12, 1237. 

3 C. Graebe, B. 31, 2976. 

4P. Friedlander and J. Neuddrfer, /6zd. 30, 1081. Cf. M. 109, 42. 
5 H. Schiff, oid. 12, 1531. Ann. 154, II. 


DETERMINATION OF HYDROXYL. 15 


remove. The magnesia is prepared from the sulphate 
or chloride, which must be free from iron; the solu- 
tion is treated with alkali hydroxide in quantity insuff- 
cient to cause complete precipitation; after thorough 
washing the magnesia is retained as a paste under 
water. The acetyl derivative (I-1.5 grams) is inti- 
mately mixed with the magnesia paste (about 5 grams) 
and a little water, and transferred, together with water 
(100 cc.), to a flask of resistant glass. The mixture is 
boiled in a reflux apparatus during 4-6 hours, although 
usually the hydrolysis is completed in 2-3 hours. The 
liquid is concentrated in the flask to a third of its orig- 
inal volume, cooled, filtered by means of a pump, the 
insoluble portion washed, and the filtrate and wash- 
ings treated with ammonium chloride, ammonium 
hydroxide, and ammoniacal sodium phosphate. The 
magnesium ammonium phosphate, after standing during 
twelve hours, is filtered, dissolved in dilute hydrochlo- 
ric acid, and reprecipitated by means of ammonium 
hydrate; 1 part of Mg,P,O, = 0.774648 parts of C,H,O. 
The solubility of magnesia in highly dilute solutions of 
magnesium acetate is too small to require a correction. 
Even ‘‘insoluble’’ acetyl derivatives may be hydro- 
lysed by magnesia, provided that they are in a finely 
divided state, the boiling being prolonged to twelve 
hours if necessary. The magnesia method is advan- 
tageous in cases where the use of alkali causes decom- 
position and the production of colored substances 
which render titration uncertain. 

(¢) If hydrochloric acid (sulphuric acid) is without 
action on the hydroxyl compound, the acetyl deriva- 
tive is heated with a known quantity of N/I acid ina 


16 RADICLES IN CARBON COMPOUNDS. 


sealed tube or pressure-flask at 120°—150°, and the lib- 
erated acetic acid titrated.! 

(4) Hydrolysis by means of sulphuric acid is es- 
pecially advantageous when the original substance is 
insoluble in it. The acid employed should be free 
from oxides of nitrogen and contain 75 parts of con- 
centrated acid in 32 parts of water. The dilute acid 
(10 cc.) is mixed in a flask with a weighed quantity of 
the, acetyl derivative (about I gram), which, if neces- 
sary, may be previously moistened with three or four 
drops of alcohol; the mixture is warmed on a hot, but 
not boiling, water-bath for a half hour, diluted with 
eight volumes of water, then boiled during 3—4 hours 
on the water-bath, and allowed to remain during 
twenty-four hours at the ordinary temperature. The 
precipitated hydroxyl derivative is then collected on a 
filter.**- Should the hydroxyl derivative not be com- 
pletely insoluble in the dilute acid a blank experiment 
must be made and the correction introduced.® 

(z) The following process‘ is stated to be universally 
applicable. The acetyl derivative (0.2-0.4 gram) is 
placed in the flask A, Fig. 1, together with dilute (2 
acid: I water) sulphuric acid (3 cc.); after some time 
water (3 cc.) is added. The mixture is heated at 
60°—70° until complete hydrolysis is effected. Meta- 
phosphoric acid solution (20 cc.) containing 100 grams 





1 Schitzenberger, Ann. de Ch. Ph. 84, 74. Herzfeld, B. 13, 266. 
Schmoeger, /é7d. 25, 1453. 

2 Liebermann, B. 17, 1682. Herzig, M. 6, 867-890. 

3 Ciamician and Silber, B. 28, 1395. 

*F. Wenzel, M. 18 (1897), 659; 19, 22. Journ. Chem. Soc. 74, i. 
(1898), 234. 


~ 


DETERMINATION OF HYDROXYL. 17 


acid and 450 grams cryst. disodium phosphate in 1 liter 
of water is added, the flask A connected with the 
hydrogen generating apparatus and distilled to dryness 
under greatly reduced pressure. Water (20 cc.) is 











ce OF THE 
UNIVERSIT 
OF 

















EER, 























aie 
WS 





added and the distillation repeated. The apparatus is 
now filled with hydrogen, the pump-flask B, which con- 


ty , 
tains [> potassium hydroxide, and its condenser are 


disconnected and the excess of alkali determined by 
titration. During the distillation the flask C is heated 
in water to the temperature of A; it serves to retain 
traces of phosphoric acid. The distillate must be free 


BRARD 


Se 


~\ 


Y \ } 
U 


RECS ee 
from sulphurous acid when titrated against a iodine; if 


18 RADICLES IN CARBON COMPOUNDS. 


this is not the case the sulphuric acid used for hy- 
drolysis must be diluted. Halogen and sulphur com- 
pounds must be mixed, before hydrolysis, with silver 
sulphate and cadmium sulphate respectively. 

(7) Hydriodic acid has also been eine yee for the’ 
hydrolysis of acetyl derivatives. 

Unhydrolysable acetyl compounds derived from 
orthoaminobenzaldehyde have been described.? 


(B) Additive Method.’ 


This may be regarded as complementary to the 
method described under # In cases where the acetyl 
derivative is insoluble in cold water, and the acetyla- 
tion proceeds quantitatively, the yield of product from 
a given weight of hydroxyl compound gives a meas- 
ure of the number of acetyl groups introduced. The 
method has recently been applied to the investigation | 
of the acetylation products of tannic acid. 


(C) Weighing the Potassium Acetate.® 


This method is applicable to compounds yielding. 
potassium salts insoluble in absolute alcohol. The 
acetyl derivative (1-2 grams) is boiled with a slight 
excess of potassium hydroxide solution until it is com- 
pletely hydrolysed, water being added to replace that 
evaporated. The remaining alkali is neutralized with 
carbonic anhydride, the liquid evaporated as completely 





1 Ciamician, B. 27, 421, 1630. 

2 R. Pschorr, /é¢d. 31 (1898), 1289. 

3 Goldschmiedt and Hemmelmayr, M. 15, 321. 
4H. Schiff, Ch. Ztg. 20, 865. 

5 Wislicenus, Ann. 129, 181. 


DETERMINATION OF HYDROXYL. 19 


as possible on the water-bath, and the residue thor- 
oughly extracted with absolute alcohol. The alcoholic 
solution is evaporated to dryness and the residue again 
extracted, any insoluble matter being removed and 
well washed, and the liquid evaporated in a tared ves- 
sel. The dried potassium acetate remaining is then 
cautiously fused, allowed to cool over sulphuric acid, 
and weighed. 


(D) Distillation Method. 


Fresenius! first suggested that the acetic acid from 
acetates could be liberated with phosophoric acid and 
determined by distillation, with or without the help of 
steam. The method was then applied by various 
chemists to the hydrolysis of acetyl derivatives, but 
since they replaced the phosphoric acid by sulphuric 
acid their results were not satisfactory. Subsequently 
the use of phosphoric acid was again proposed*. The 
acetyl product is hydrolysed by means of alkalis or 
barium hydroxide, acidified at the ordinary tempera- 
‘ture with phosphoric acid, filtered, and well washed; 
the filtrate and washings are then distilled until the 
distillate is completely free from acid, fresh water being 
introduced into the retort from time to time as may 
be necessary. The distillation is at first carried out 
over a flame and subsequently from an oil-bath, the 
temperature being allowed to rise to I140°-150°, ora 
water-bath may be employed, in which case the pres- 





1Z. anal. Ch. 5; 31§:-14, 172. 

2 Erdmann and Schulze, Ann. 216, 232. Buchka and Erk, B. 18, 
1142. Schall, /éd. 22, 1561, 

% Herzig, M. 5, 90. 


20 RADICLES IN CARBON COMPOUNDS. 


sure is reduced.' The connections must all be of 
caoutchouc, as corks would absorb acetic acid, and the 
alkali and acid employed must be free from nitrates or 
nitrites. The presence of chlorides is not hurtful, as 
these do not liberate hydrogen chloride in the presence 
of the phosphoric acid, which is one advantage it pos- 
sesses over sulphuric acid.* The distillate is treated 
with baryta water in excess, and concentrated in a 
platinum dish, the excess of barium removed by means 
of carbonic anhydride, and the filtrate evaporated to 
dryness; water is then added, the liquid filtered, the 
insoluble portion well washed, and the barium in the 
filtrate and washings determined as sulphate; I gram 
BaSO, = 0.5064 gram C,H,O, or 0.5070 gram C,H,O,. 

The acetyl groups in acetylated gallic acids*® were 
determined by mixing the substance (3—4 grams) with 
pure alcohol (5 cc.) and sodium hydroxide (2-3 grams) | 
dissolved in water (15 cc.). After the hydrolysis was 
completed, the alcohol was dissipated, the residue acidi- 
fied with phosphoric acid, the acetic acid driven over 
in a current of steam, and its amount determined by 
titrating the distillate with sodium hydroxide solution, 
phenolphthalein being used as indicator. One source 
of error in this method arises from carbonic anhydride, 
which is always present in the sodium hydroxide, and 
is often produced by the hydrolysis itself; it volatil- 
izes together with the acetic acid. The difficulty 
may be avoided by heating the neutralized liquid to 
boiling, adding a very small quantity of N/1 acid, 





1H. A. Michael, B. 27, 2686. 
2R. and H. Meyer, /ézd. 28, 2967. 
8 P. Sisley, Bull. Soc. Chim. III. 11, 562. Z. anal. Ch. 34, 466. 


DETERMINATION OF HYDROXYL. 21 


again boiling, and then neutralizing, the process being 
repeated until the neutralized liquid ceases to become 
red on boiling; this shows that all the carbonates are 
decomposed and no loss of acetic acid need be appre- 
hended. It has been suggested! that, after the hy- 
drolysis, elimination of the alcohol, and acidification by 
means of phosphoric acid, the liquid should be boiled 
in a reflux apparatus until the carbonic anhydride is re- 
moved, the subsequent operations being similar to 
those above described. Sources of error in this method 
are described on p. 30.? | 


BENZOYL DERIVATIVES. 
(I) PREPARATION OF BENZOYL DERIVATIVES. 


The following reagents are employed for the intro- 
duction of the benzoyl radicle into hydroxyl com- 
pounds: 

Benzoyl chloride; 

Benzotu anhydride, sodium benzoate; 

p-Brombenzoyl chloride, p-Brombenzoic anhydride; 

o-Brombenzoyl chloride, 

m-Nitrobenzoyl chloride; 

Phenylsulphonic chloride. 


(A) Preparation of Benzoyl Derivatives by Means of 
Benzoyl Chloride. 


(a) The ‘‘acid ’’ method consists in heating the sub- 
stance with the chloride at 180° during several hours 





1 P, Dobriner, Z. anal. Ch. 34, 466, foot-note. 
2 Cf. G. Goldschmiedt and R. Jahoda, M. 13, 53; Goldschmiedt and 
Hemmelmayr, /éid. 14, 214; 15, 319. 


22 RADICLES IN CARBON COMPOUNDS. 


in a reflux apparatus; it is not advisable to employ a 
sealed tube unless there is assurance that the hydro- 
chloric acid will not cause secondary reactions nor, in 
the case of nitrogenous compounds, combine with them 
to form hydrochlorides which would then cease to 
react;! when this may occur the calculated quantity of 
chloride is employed, and the heating continued during 
about four hours at 100°—110°. 

(2) The preceding method has been largely super- 
seded by the use of the chloride in dilute aqueous alka- 
line solution.2 It has been widely applied, is usually 
known as the Schotten-Baumann method, and seldom 
fails to give good results. The substance is well 
shaken with sodium hydroxide solution (10%) and ben- 
zoyl chloride in excess until the smell of the latter is 
no longer noticeable.‘ If the benzoylation is to be as 
complete as possible more concentrated alkali should be ~ 
used, say fifty parts of sodium hydroxide solution (20%) 
and six parts of the chloride in a closed flask. The tem- 
perature should not exceed 25°,° and it is frequently de- 
sirable to add the alkali and chloride alternately little by 
little, whilst in some cases the former must be highly di- 
lute (0.25%)." It has also been found to be advisable to 
use the reagents in the proportion of seven molecules 
of soda and five of the chloride to each hydroxyl; the 
alkali is dissolved in water (8—10 parts), and the shak- 
ing and gentle cooling continued for 10-15 minutes. 





1 Danckwortt, Arch. Pharm. 228, 581. 

2 Lossen, Ann. 161, 348; 175, 274, 319; 205, 282; 217, 16; 265, 
148, foot-note. 

3’ Baumann, B. 19, 3218. # Baumann. 

5 Panormow, B. 24, R. 971. 6 y, Pechmann, Jd. 25, 1045. 

7B. 31, 1598. 8 Skraup, M. 10, 390. 


DETERMINATION OF HYDROXYL. 23 


Hexabenzoylruberythric acid is obtained by use of a 
IO per cent. sodium hydroxide solution but a solution 
1:8 yields a heptabenzoyl derivative.’ For experi- 
ments with pyragallol the flask must be filled with coal- 
gas; in the case of substances which are unstable in 
presence of caustic alkali, sodium carbonate,’ bicar- 
bonate, or sodium acetate may be used.? In some 
cases it is advantageous to dissolve the substance in 
pyridine and then add the benzoyl chloride; occasionally 
a higher acyl derivative is obtained in this manner than 
by the use of sodium hydroxide. The method is par- 
ticularly well adapted to bodies which are unstable in 
presence of alkali. The precipitated benzoyl deriva- 
tives are usually white and semi-solid, and gradually 
harden and crystallize by prolonged contact with 
water; often traces of benzoyl chloride or benzoic 
acid are retained with great tenacity. For the purifi- 
cation of the benzoyl derivative of glucose® it was 
necessary to dissolve out the crude product with ether; 
this was distilled off, and the residue treated with alco- 
hol, which decomposed the last portions of benzoyl 
chloride that had not been removed by prolonged shak- 
ing of the ethereal solution with concentrated alkali. 
The alcoholic liquid was treated with soda in excess, 
precipitated with water, and the alcohol and ethylic 
benzoate removed by means of steam. The residue 
was then repeatedly recrystallized; at first from alco- 
hol, then from glacial acetic acid. The pure com- 

1 Schunck and Marchlewski, Journ. Chem. Soc. 65 (1894), 187. 

* Lossen, Ann. 265, 148. 

3’ Bamberger, M. & J., II., p. 546. E. Fischer, B. 32 (1899), 2454. 


4 A. Einhorn and F. Hollandt, Ann. 301 (1898), 95. 
5 Skraup, M. 10, 395. 





24 RADICLES IN CARBON COMPOUNDS. 


pound is insoluble in ether, whilst the crude preparation 
readily dissolves. Benzoic acid may be frequently re- 
moved by sublimation in vacuo, or by extraction with 
boiling carbon bisulphide.t’ Repeated extraction with 
alkali is usually effective for the purification of benzoyl 
derivatives soluble in ether, but it may produce partial 
hydrolysis. Derivatives insoluble in ether may be ex- 
tracted with this in order to remove excess of benzoyl 
chloride and benzoic anhydride.?, Commercial benzoyl 
chloride often contains chlorobenzoyl chloride,® and 
since the chlorobenzoyl derivatives are less soluble 
than the benzoyl derivatives, recrystallization is not 
adequate to secure a product free from chlorine. It 
appears also that pure benzoyl chloride may yield 
chloro-derivatives.4 Benzotrichloride may contain 
benzal chloride; during the conversion of the former 
into benzoyl chloride by the action of lead oxide or 
zinc oxide the latter may yield benzaldehyde, the 
presence of which would cause complications.’ Lac- 
_ tones often yield benzoyl derivatives of acids which are 
soluble in alkali; they are separated by acidifying and 
removing the benzoic acid from the precipitate by 
steam distillation.® 

Schotten-Baumann’s method has also been applied 
to the preparation of acetyl derivatives, but with com- 
paratively little success on account of the greater in- 
stability of acetyl chloride in the presence of alkali or 
water.’ 





1 Barth and Schreder, M. 3, 800. 2M. Jaffe, B. 35 (1902), 2899. 
$V. Meyer, B. 24, 4251. Goldschmiedt, M. 13, 55, foot-note. 
*B..-26, 20¢7, 5 Hoffmann and V. Meyer, /éid. 25, 209. 
6 Ibid. 30, 127. 1 [bid. 27, 3183. 


~ 


DETERMINATION OF HYDROXYL. 25 


(c) Benzoyl derivatives may also be prepared in 
ethereal or benzene solution, with the help of dry alkali 
carbonate,’ or of tertiary bases such as quinoline, pyri- 
dine, or dimethyl aniline.*> (Cl p: 7.) 

(2) Sodium ethoxide* may also be employed for the 
decomposition of benzoyl chloride, and it was only in 
this manner that the benzoyl derivative of diacetylace- 
tone could be obtained.‘ The ketone was heated in a 
reflux apparatus during six hours, with two molecular 
proportions each of benzoyl chloride and sodium 
ethoxide, which had been dried at 200°; after cooling, 
the sodium chloride and benzene were removed, the 
residue dissolved in ether, and the solution shaken 
with dilute alkali. 

(e) Pyridine or quinoline may be used in place of 
aqueous, or alcoholic alkali.» The product is triturated 
with dilute hydochloric acid and recrystallized from 
alcohol. 


(B) Preparation of Benzoyl Derivatives from Benzoic 
Anhydride. 

(2) The hydroxyl compound is heated with benzoic 
anhydride, in an open vessel, at 150° during 1-2 
hours.® This is often preferable to method 0.‘ 

(6) In some cases the use of benzoic anhydride and 
sodium benzoate produces a more complete acylation 





1 Hoffmann and V. Meyer, B. 27, 3183. 

2 L. Claisen, /bzd. 31, 1023. ° 

+L. Claisen. 

4 Feist, B. 28, 1824. 

5 Deninger, /éid. 28, 1322; A. Einhorn and F. Hollandt, Ann. 301, 
(1898) 95. 

6 Liebermann, Ann. 169, 237. 

7L. Sherman Davis, Arch, Pharm. 235 (1897), 213. 


26 RADICLES IN CARBON COMPOUNDS. 


than Schotten-Baumann’s method. As an example 
of its use, scoparin (2 grams), benzoic anhydride (10 
grams), and dry sodium benzoate (1 gram) were heated 
in an oil-bath at 190° during six hours; the product 
was treated at the ordinary temperature overnight with 
aqueous sodium hydroxide (2%), and the precipitated 
hexabenzoyl derivative purified by means of alcohol. 


(C) Preparation of Substituted Benzoic Acid Derivatives 
and of Phenylsulphonic Chloride.’ 


(2) Parabromobenzoyl chloride. — Parabromoben- 
zoic acid is intimately mixed with the equivalent quan- 
tity of phosphorus pentachloride, and warmed until the 
evolution of hydrogen chloride slackens. The product 
is then fractionated under reduced pressure; the pure 
compound melts at 42°, boils at 174° (102 mm), and 
is readily soluble in benzene and light petroleum. 

(6) Parabromobenzoic anhydride* is prepared by 
heating sodium parabromobenzoate (3 parts) with para- 
bromobenzoyl chloride (2 parts) at 200° during an 
hour. It melts at 212°, is almost insoluble in ether, 
carbon bisulphide, and glacial acetic acid, dissolves 
slightly in benzene, and is purified by recrystallization 
from chloroform. 

(c) Orthobromobenzoyl chloride * is prepared in a man- 
ner similar to its isomer. It is a liquid, boiling at 
241°-243°, and may be distilled under the ey 
pressure without decomposition. 





1 Goldschmiedt and Hemmelmayr, M. 15, 327. 

2 J. J. Sudborough, Journ. Chem. Soc. 67 (1899), 589. 

5 B. a1, 2244. * Schotten and Schlémann, /ézd, 24, 3680. 
5 [bid. 21, 2244. Schépf, Zézd. 23, 3436. 


~ 


DETERMINATION : OF HYDROXYL. 27 


(a2) Metanitrobenzoyl chloride’ is formed from the 
nitrobenzoic acid by gradually and intimately mixing 
with it the requisite amount of phosphorus pentachlo- 
ride; the phosphorus oxychloride is removed by dis- 
tillation, and the residue fractionated under reduced 
pressure. It melts at 34° and boils at 183°-184° 
(50-55 mm). 

(e) Phenylsulphonic chloride* is obtained by heating 
sodium phenylsulphonate with phosphorus penta- 
chloride in equivalent proportion; when the action 
ceases the product is poured into water, the oily por- 
tion removed, washed with water, dissolved in ether, 
and the solution decolorized by: treatment with animal 
charcoal. The compound melts at 14° and boils at 
120° (10 mm). 


(D) Acylation by Means of Substituted Benzoic Acid 
Derivatives and of Phenylsulphonic Chlorides. 


(a) Parabromobenzoyl chloride, or parabromobenzoic 
anyhdride, has been used for acylation, the number of 
the original hydroxyl groups being determined from 
the bromine content of the product. 

(6) Orthobromobenzoyl chloride* and metanttroben- 
goyl chloride® are also well adapted for the determina- 
tion of hydroxyl groups. 

(c) Phenylsulphonic chloride *® has been employed for 





1 Claisen and Thompson, B. 12, 1943. 

2 Otto, Z. f. Ch. 1866, 106. 

3 F. Loring Jackson and G. W. Rolfe, Am. Chem. Journ. g, 82; B. 
20, R. 524. 

4Schotten, /ézd. 21, 2250. 

5 Claisen and Thompson, /ézd, 12, 1943. Schotten, /zd. 21, 2244. 

6 Hinsberg, /ézd. 23, 2962. Schotten and Schlémann, /ézd. 24, 3689. 


28 RADICLES IN CARBON COMPOUNDS. 


the same purpose!; it is either allowed to act like the 
benzoyl chloride in the Schotten-Baumann method, or 
it is warmed with the hydroxyl compound (phenol) 
and zinc dust, or zinc chloride.? 

Phenylsulphonic derivatives are often more stable 
than the corresponding benzoyl compounds.* 


ANALYSIS OF BENZOYL DERIVATIVES. 


(a) The exact number of benzoyl groups in many 
benzoyl] derivatives is shown by their elementary analy- 
sis; in substitution products the amount of haloid, nitro- 
gen, or sulphur is determined. 

(4) The following method has been suggested for 
the direct determination of the benzoic acid: 4 The sub- 
stance (about 0.5 gram) is hydrolysed by heating it 
during two hours at 100°, in a sealed tube, with con- 
centrated hydrochloric acid (10 parts), which has been 
saturated with benzoic acid at the ordinary tempera- 
ture. The product is allowed to remain 1-2 days at 
the ordinary temperature, filtered by means of the 
pump, and the precipitate washed, at first with more 
of the hydrochloric acid, then with a saturated aqueous 
solution of benzoic acid. The purified benzoic acid is 
now dissolved in N/r1o sodium hydroxide solution in 
excess, titrated with excess of acid, and the neutraliza- 
tion effected with the needful quantity of the soda solu- 
tion. The latter is standardized against pure benzoic 
acid, phenolphthalein being employed as the indicator. 
The admixture of the acid and water during the wash- 





1M. Georgescu, B. 24 (1891), 416. ?C. Schiaparelli, Gazz. 11, 65. 
3B. 30, 669. 4G, Pum, M. 12, 438. 


DETERMINATION OF HYDROXYL. 29 


ing of the benzoic acid always causes a precipitation of 
benzoic acid, so that the results obtained by this 
method are invariably about 1 per cent. too high; 
therefore, this amount must be deducted from the per- 
centage of acid found, or the exact correction ascer- 
tained by means of a blank experiment with the same 
quantities of liquids as have been used in the main one. 

(c) A method of more general application consists 
in separating the benzoic acid from the hydrolysed 
substance by means of a current of steam, and titrating 
the distillate;! its principle is therefore identical with 
that involved in the determination of acetyl groups, 
and it presupposes that the compound under examina- 
tion is completely hydrolysed by alkalis, and yields no 
acid, other than benzoic, volatile with steam. The 
substance (about 0.5 gram) is mixed with alcohol 
(30-50 cc) and potassium hydroxide in excess, and 
heated in a reflux apparatus; when the hydrolysis is 
completed the product is cooled, acidified with concen- 
trated phosphoric acid solution, or vitreous phosphoric 
acid, and distilled in a current of steam. The distilla- 
tion is conducted slowly at first, and alcohol added, if 
necessary, by means of a dropping funnel, the object 
being to secure the gradual deposition, in a crystalline 
state, of the hydrolysis products, as otherwise resinous 
substances might surround the benzoic acid and con- 
siderably hinder its volatilization. When the distillate 
measures I—I.5 liters, the following 150 cc. are col- 
lected separately and tested for benzoic acid by titra- 
tion, and, as soon as it is no longer present, the 





1 R. and H. Meyer, B. 28, 2965. 


30 RADICLES IN CARBON COMPOUNDS. 


distillation is stopped. The combined distillate is ren- 
dered alkaline with a known quantity of N/1o sodium 
hydroxide solution, standardized against pure benzoic 
acid, and evaporated in a platinum, silver, or nickel 
dish to a volume of 100-150 cc., when the excess of 
alkali is titrated back, the liquid being boiled to ex- 
pel carbonic anhydride; this may be regarded as accom- 
plished when boiling for ten minutes produces no 
change in the indicator, which is aurin or rosolic acid. 
In order to guard against the production of sulphites 
and sulphates, the concentration of the alkaline liquid 
is carried out by means of a spirit or petroleum lamp, 
unless a special gas burner is available. 

(2) Benzoylmorphine has been examined by direct 
titration.! The substance was dissolved in methylic 
alcohol, mixed with a little water, normal sodium 
hydroxide solution (100 cc.) added, and boiled in a 
reflux apparatus until a portion of it gave no turbidity 
with water; titration with normal hydrochloric acid, in 
presence of phenolphthalein, showed that the original 
compound was the monobenzoyl derivative. The 
same method was successfully applied to the analysis 
of dibenzoylpseudomorphine and_ tribenzoylmethyl- 
pseudomorphine. 


ACYLATION BY MEANS OF OTHER ACID 
RADICLES. 

Propionic anhydride, isobutyric anhydride, opianic 

acid,” stearic anhydride,’ and phenylacetyl chloride 





1 Vongerichten, Ann. 294, 215. Cf. Knorr, B. 30, 917-920, 
2 B. 31, 358. 5 Ann. 262, 5. 


DETERMINATION OF HYDROXYL. 3I 


are sometimes used for acylation, as their relatively 
high boiling points facilitate their reaction with the 
hydroxyl compound. 

(a) Propionyl derivatives are Sree by heating 
the substance with propionic anhydride, in a stout, 
closed bottle, at 100° during two hours; an open ves- 
sel may also be employed, and the reaction started by 
the addition of a drop of concentrated sulphuric acid. 

(6) Lsobutyryl derivatives are prepared in a similar 
manner. Isobutyryl ostruthin was prepared by heating 
ostruthin (3 grams) with isobutyric anhydride (10 
grams) in a sealed tube at 150° during 3 hours. The 
product was poured into water, allowed to remain until 
it became crystalline, washed with warm water until 
neutral, pressed, dried by means of filter paper, and 
recrystallized from alcohol.’ 

(c) Phenylacetyl chloride is prepared* by adding the 
acid, in chloroform solution, to well-cooled phosphorus 
pentachloride, and is used‘ like benzoyl chloride in 
Schotten-Baumann’s method, the substance being 
dissolved in dilute aqueous potassium hydroxide solu- 
tion, and well shaken with excess of the chloride. 

(2) The extent to which phosphoric acid may prove 
useful remains at present undetermined.°® 


ALKYLATION:- OF TY DROXVIL-GROUPS. 


The hydroxyl of phenol and primary alcohols is 
capable of alkylation, and the number of alkyl groups 





1 Arch. Pharm, 228, 127; Fortner and Skraup, M. 15 (1894), 200. 

2 Jassoy, Jézd. 228, 551. 

3 B. 20, 1389; 29, 1986; H. Metzner, Ann. 298 (1897), 375. 

4 Hinsberg, B. 23, 2962. ° Lbid, 30, 2368; 31, 1094, 


32 RADICLES IN CARBON COMPOUNDS. 


introduced may be determined from the resulting ethers 
by Zeisel’s method (cf. p. 38). Asarule, the phenolic 
ethers are not hydrolysed by alkalies (cf. p. 53), hence 
it is possible to differentiate between the hydroxyl and 
carboxyl of the hydroxy acids. It has, however, 
been shown that the use of potassium hydroxide and 
alkyl iodides may lead to the production of compounds 
with the alkyl directly linked to carbon,’ and that, on 
the other hand, hydroxy] in the ortho position relative 
to carbonyl oxygen is determinable by acylation, but 
not by alkylation.’ 

Dimethy] sulphate is sometimes preferable to methyl- 
iodide for the alkylation of phenols and all other 
classes of compounds capable of alkylation. With 
phenols it is employed in alkaline aqueous solution as 
in the Schotten-Baumann method ® (cf p. 22). 

Diazomethane may also be used as an alkylating 
agent.* 


PREPARATION OF BENZYL DERIVATIVES. 


Benzyl ethers of phenols are prepared by heating 
the latter in a reflux apparatus, during several hours, 
with the calculated quantities of sodium ethoxide and 
benzyl chloride in alcoholic solution; the precipitated 
sodium chloride is removed by filtration from the hot 





1 Herzig and Zeisel, M. 9, 217, 882; 10, 144, 735; 11, 291, 311, 413; 
14, 376. 

2 Graebe. Ilerzig, M. 5,72. Schunk and Marchlewsky, Journ. Chem, 
Soc. 65, 185. Kostanecki, B. 26, 71, 2901. Perkin, Journ. Chem. Soc. 
67, 995; 69, Sor. 

3 F, Ullmann and P. Wenner, B. 33 (1900), 2476, 

4y. Pechmann, /id. 28, 856; 31, 64, 501, Ch. Ztg. 98, 142. 


~ 


DETERMINATION OF HYDROXYL. 33 


liquid,! and the composition of the ether determined 
by elementary analysis. Where the chloride fails to 
react, either in the manner described, or jn conjunction 
with the silver salt of the phenol, benzyl iodide may 
be employed for the preparation of these compounds.* 


ESTERIFICATION: OF PHENOLS. 


Mono-, di-, and trihydric phenols easily yield read- 
ily crystallizable esters with phenylnitrocinnamic or 
phenylcinnamic acid, in presence of phosphoric anhy- 
dride and a neutral solvent. The reaction increases 
in energy with the number of hydroxyl groups and 
therefore a solvent of high boiling point, such as 
toluene, should be employed with tri- and dihydric 
phenols. Ifthe latter are in excess they yield only 
monoesters.® 


PREPARATION OF CARBAMATES BY MEANS 
OF CARBAMYL CHLORIDE. 


PREPARATION OF CARBAMYL CHLORIDE.! 


Ammonium chloride is placed in a distillation flask 
attached to a long and wide condenser, heated at about 
400° in an air bath, and treated with a current of car- 
bonyl chloride, dried by means of sulphuric acid. The 
carbamyl chloride, which has a highly offensive smell, 
distils over and condenses to a colorless liquid, or to 





1 Haller and Guyot, C. r. 116, 43. 

2M, & J. Il., p. 125. K. Auwers and A. J. Walker, B. 31 (1899), 
3040, 

3M. Bakunin Gazz, 34 (1902), i. 178. 

4 Gattermann & G. Schmidt. B. 20, 858. 


34 RADICLES IN CARBON COMPOUNDS. 


long, broad needles melting at 50°. It volatilizes at 
61°-62°, and, after prolonged standing, polymerizes 
to cyamelide, for which reason it should be employed 
as quickly as possible after its preparation. In contact 
with water or moist air, it is hydrolysed to carbonic 
anhydride and ammonium chloride. 


PREPARATION OF CARBAMATES. 


Carbamyl chloride reacts with hydroxyl] derivatives 
in accordance with the equation: 


NH,.CO.Cl + HO.R > NH,.CO.OR + HCl, 


the resulting carbamates crystallize readily.’ It is 
usually only necessary to mix the substances, in equiv- 
alent proportion, in ethereal solution, as the reaction 
generally proceeds quantitatively at the ordinary tem- 
perature; in the case of some polybasic phenols gentle ~ 
warming is requisite. The amount of nitrogen in the 
product is a measure of the number of hydroxyl groups 
in the original compound. Great excess of the chloride 


should not be used, as it may lead to the production of 
ethereal allophanates, NH,.CO.NH.CO.OR. 


PREPARATION OF DIPHENYLCARBAMYL 
CHLORIDE (C,H,), N.CO Cl. 


This substance has been found especially useful in 
the investigation of rhodinol (geraniol).* It is prepared 
by dissolving diphenylamine (250 grams) in chloroform 
(700 cc), adding anhydrous pyridine (120 cc.), and 





1 Gattermann, Ann, 244, 38. 
2 Erdmann and Huth, J. pr. 53, 45: 


~ 


DETERMINATION OF HYDROXYL. 35 


passing a current of carbonyl chloride (147 grams) 
into the liquid, which is maintained ato°. After re- 
maining during 5-6 hours, the chloroform is distilled 
off on the water-bath, and the residue crystallized 
from alcohol (1.5 liters). The yield is 300 grams, 
the product, after recrystallization from alcohol (1 
liter), is pure, and melts at 84°.! 


PREPARATION OF PHENYLCARBAMIC ACID 
DERIVATIVES. 


PREPARATION OF PHENYLISOCYANATE.* 


Commercial phenylurethane (15 grams) is mixed with 
phosphoric anhydride (30 grams) in a small retort, and 
heated by means of a luminous flame, a large distilla- 
tion flask being employed as receiver; the combined 
distillate from a number of such preparations is then 
fractionated once. The isocyanate boils at 169° (769 
mm),° and the yield is 52~53 per cent. 


ACTION OF PHENYLISOCYANATE ON HYDROXYL 
DERIVATIVES.® 


Ethereal phenylcarbamates are formed by the inter- 
action of hydroxyl compounds and phenylisocyanate in 
equimolecular proportion in accordance with the 
equation : 


R.HO + C,H,N: CO->C,H,NH.CO.OR. 





1 J. pr. 56, 7- 

2 H. Goldschmiedt, B. 25, 2578, foot-note. 

% Hofmann, /é7d. 18, 764. 

* Zanoli, /bid. 25, 2578, foot-note. 

® Hofmann, Ann. 74, 3; B. 18, 518. Snape, /id. 18, 2428. 


30 RADICLES IN CARBON COMPOUNDS. 


The reaction often proceeds at the ordinary tempera- 
ture, but it is best to mix the compounds in the re- 
quisite proportion, and boil them rapidly by means of a 
previously heated sand-bath, and complete the reac- 
tion by shaking and gentle warmth. Polybasic phe- 
nols are heated in a sealed tube for 10-16 hours; ? if the 
compound. eliminates water at this temperature the 
phenylisocyanate is converted by it into carbonic an- 
hydride and carbanilide.* The duration of the boiling 
in an open vessel should be shortened as much as pos- 
sible to reduce the production of diphenylcarbamide. 
When cold the product of the reaction is treated with 
a little benzene or ether to dissolve unaltered phe- 
nylisocyanate, then washed with cold water, and re- 
crystallized from alcohol, ethylic acetate, or a mixture 
of ether and light petroleum, which leaves the sparingly 
soluble. diphenylcarbamide undissolved. 

a—2-Acetylangelica lactone reacts slowly with phe- 
nylisocyanate at the ordinary temperature. After 14 
days the product is boiled out with benzene to sep- 
arate it from #-derivate and precipitated by means of 
light petroleum. It is decomposed by alcohol. 

The presence of negative groups in the molecule of 
- the hydroxy] derivative hinders, or completely prevents, 
the reaction; thus trinitrophenol gives no derivative 
when heated at 180° under pressure.* Ketodibenzoyl- 
methane also fails to form a urethane but yields a 





1 Tessmer, B. 18, 960. 

2 Snape, /did. 18, 2428. 

3 Tessmer, /did. 18, 969. Beckmann, Ann. 292, 16. 
4L. Knorr and W, A, Caspari, /é7d. 303 (1898), 141. 
5 Gumpert, J. pr. 31, 119; 32, 278. 


DETERMINATION OF HYDROXYL. 37 


small amount of triphenylisocyanurate.'. An anomal- 
ous action of phenylisocyanate has been described. 

Phenylisocyanate combines with certain mercap- 
tans, forming compounds with the group SH analogous 
to those yielded with hydroxyl derivatives, hence, in 
dealing with sulphur derivatives, the results obtained 
from its use must be interpreted with caution.° 

An attempt has been made to determine the pres- 
ence of hydroxyl groups by the use of 1:2: 4-chlordini- 
trobenzene.* eae 

Organic magnesium derivatives react with many 
hydroxyl derivatives in accordancé with the equation 
CH,MglI + R.OH —CH,+ RO.MglI. The products 
are frequently crystalline. Compounds free from hy- 
droxyl groups do not react with alkylmagnesium 
halides. The reaction is carried out in presence of 
anhydrous ether, and is useful for the identification of 
hydroxyl derivatives, and their separation from mix- 
tures of hydrocarbons, etc.°® 





1 J. Wislicenus, Ann. 308 (1899), 233. 

2 U. Eckart, Arch, Pharm, 229 (1891), 369. 

3 H. Goldschmidt and A. Meissler, B, 23 (1890), 272. 
* Vongerichten, Ann. 294, 215. 
5 L. Tschugaeff, B. 35 (1902), 3912. 


CHAPTER II. 


DETERMINATION OF METHOXYL, CH,O-, ETHOXYL, 
C,H,O-, AND CARBOXYL, CO.OH. 


DETERMINATION OF METHOXYL, CH,O-. 


S. ZEISEL’S METHOD.! 


This method, which is distinguished for beauty and 
reliability, depends on the conversion of the methyl of 
the methoxy group into methyl iodide by means of 
hydriodic acid, the methyl iodide being then decom- 
posed by alcoholic silver nitrate solution into silver 
iodide. The original apparatus, represented in Fig. 2, 
consists of a reversed condenser A, through which 
water at 40°—50° flows; at the lower end a flask 4 of 
30-35 cc. capacity is attached by means of a cork; the 
flask has a side tube sealed on,through which a current 
of carbonic anhydride may be passed. A Geissler’s 
potash bulb is connected to the upper end of the con- 
denser, also by means of a cork; it contains 0.25-0.5 
gram red phosphorus suspended in water, and is 
maintained at a temperature of 50°-60° by the water- 
bath in which it is placed. Its object is to absorb any 





1M. 6, 989; 7, 406. 
38 


~ 


METHOXYL, ETHOXYL, AND CARBOXYL. 39 


iodine or hydriodic acid which might be carried over 
by the methyl iodide vapor. The two flasks which 












































AD 
i| Pet es | 
Hi 
he 
| 
ie. ‘al 
ig! 
mI \ 


complete the apparatus have a capacity of 80 cc. each; 
the first contains 50 cc. of alcoholic silver nitrate solu- 
tion, the second 25 cc.; they are connected by means 


40 RADICLES IN CARBON COMPOUNDS. 


of corks, and may be conveniently replaced by two 
distillation flasks, the side tube of the first being bent 
downwards at a right angle into the second. A 
modified apparatus, Fig. 3, has been described, which 






























































Fic. 3. 


serves as a combined condenser and washing arrange- 
ment.!. The flask A contains the substance and hydri- 
odic acid, the bulbs // and /// red phosphorus and 
water, and B and D the silver nitrate solution. A sec- 
ond form of apparatus has a very convenient appliance 





1 Benedikt and Griissnery Ch. Ztg. 13, 872. 





sh oor is dane inte 


~ 


METHOXYL, ETHOXYL, AND CARBOXYL. 4! 


for heating and supplying the water to the condenser. 
Modified boiling flasks,* (Fig. 4) which pre- 

vent the action of the heated hydriodic acid ie 
on the cork, have been designed. 

Fig. 5 shows the latest and best form of 
Ziesel’s apparatus* and is self explanatory. 
The connections are of ground glass with 
springs and rims to make water joints. 
The flasks & and F are provided with marks 
about half-way up to indicate 45 and 5 cc re- 
spectively. If the substance under examination is 
not volatile, the condenser may be replaced by a verti- 
cal tube bent back ina U shape. The method is not 
applicable to compounds containing sulphur, and the 
hydriodic acid employed must not have been prepared 
by means of hydrogen sulphide, otherwise it is difficult 
to completely free it from volatile sulphur compounds, 
the presence of which would be apt to cause the forma- 
tion of mercaptans and silver sulphide. C. A. F. 
Kahlbaum, -of Berlin, supplies ‘‘hydriodic acid for 
methoxyl determination,’ which is prepared by means 
of phosphorus, and is trustworthy. Should a blank ex- 
periment show that the hydriodic acid produces a per- 
ceptible precipitate in the silver nitrate solution, it must 
be purified by distillation, the first and last quarters of 
the distillate being rejected; it should have a sp. 
gr. = 1.68 — 1.72. Boiling the acid with a reversed 
condenser, even during several days,‘ does not suffice 





Fic. 4. 





1L, Ehmann, Ch. Ztg. 14, 1767; 15, 221. 

? Benedikt, /é¢d. 13, 872. M. Bamberger, M. 15, 505. 
3 Made by Paul Haack of Vienna. 

* Benedikt. 


42 RADICLES IN CARBON COMPOUNDS. 


for its purification. The szlver nitrate solution is pre- 
pared by dissolving the fused salt (2 parts) in water (5 
parts), and adding absolute alcohol (45 parts); it is 








Qo 


kept in the dark, and the quantity required for each 
determination filtered into the absorption flasks. 
I. METHOD FOR NON-VOLATILE SUBSTANCES. 


After the apparatus is put together, tested, and 
. found to be air-tight, the silver nitrate solution is in- 


~ 


METHOXYL, ETHOXYL, AND CARBOXYL. 43 


troduced into the absorption flasks, and the substance 
(0.2-0.3 gram), together with the hydriodic acid (10 
cc.), placed in the distillation flask; unless Bamberger’s 
pattern is employed this should also contain a few 
pieces of porous plate to regulate the ebullition; it is 
then heated to boiling in a glycerine-bath. During 
this time the current of carbonic anhydride is passed 
through the apparatus at the rate of three bubbles in 
two seconds. The gas employed must be washed 
with water, and also with silver nitrate solution, to re 
move any hydrogen sulphide arising from impurities in 
the marble. The warm water must also be supplied 
to the condenser and the bath containing the potash 
bulbs. Some 10-15 minutes after the acid begins to 
boil the silver nitrate becomes turbid and soon a white 
double compound of silver nitrate and silver iodide pre- 
cipitates in the first flask; the liquid in the second one 
usually remains clear, but sometimes becomes opales- 
cent if the current of carbonic anhydride is very rapid, 
or the substance particularly rich in methoxyl groups; 
these conditions may also cause the precipitate to be- 
come yellow. The conclusion of the experiment is 
readily indicated by the complete subsidence of the 
precipitate, which becomes crystalline; the time re- 
quired is 1-2 hours. The tubes and flasks with the 
silver solution are disconnected, and the second one 
diluted with five parts of water; if no precipitate ap- 
pears after remaining several minutes nothing more is 
done to it, otherwise it is added to the contents of the 
first flask, which are poured into a beaker, any precipi- 
tate adhering to the tubes is removed to the beaker by 
means of a feather and jet of water; the volume is now 


44 RADICLES IN CARBON COMPOUNDS. 


made up to about 500 cc. with water, evaporated to one 
half on the water-bath, then water and a drop of nitric 
acid added, and the liquid digested until the silver 
iodide is completely precipitated; it is then filtered and 
weighed in the usual manner. The precipitate adher- 
ing to the tubes is usually dark-colored, possibly from 
the presence of a trace of phosphorus, but this does not 
affect the accuracy of the determination. 100 parts of 
silver iodide = 13.20 parts of CH,O = 6.38 parts of 
CH,. The method is applicable to compounds con- 
taining chlorine, bromine,‘ or nitro-groups, but not to 
sulphur compounds.” In the case of nitro-derivatives, 
or other compounds which readily liberate iodine from 
hydriodic acid, it is desirable to place a little red phos- 
phorus in the boiling-flask. The potash bulbs require 
refilling after four or five determinations. _Hydriodic 
acid causes many substances to become resinous, and 
the resin may protect a portion of the methoxy, com- 
pound from the action of the acid. This difficulty 
is overcome by adding acetic anhydride (6-8 volumes 
per cent) to the acid, as was shown in the case of 
methyl and acetylethylquercetin, rhamnetin, and 
triethoxyphloroglucinol.? The method is also well 
adapted for the determination of alcohol of crystal- 
lization.4 





1G, Pum, M. 14, 498. 

? Zeisel, /¢d. '7, 409. Benedikt and Bamberger, /did. 12, 1. 
3 Herzig, /bid. 9,544. Cf. Pomeranz, /did. 12, 383. 

4J. Herzig and H. Meyer, Zid. 17, 437. 


~ 


METHOXYL, ETHOXYL, AND CARBOXYL. 45 


2. MODIFICATIONS OF THE METHOD FOR ITS USE 
WITH VOLATILE COMPOUNDS. 


Volatile substances may usually be treated in the 
manner described above if, at the commencement of 
the experiment, a slow stream of carbonic anhydride 
is employed and cold water run through the condenser. 
The following special modifications for particularly 
volatile compounds have been suggested.! The sub- 
stance (O.I-0.3 gram) is sealed into a small bulb of 
thin glass, which is sealed up in a larger tube together 
with hydriodic acid Glow ee. sp. gr. = 1.7) and a piece 
of heavy glass about 2 cm in length with a sharp 
corner. The heavy glass is to assist in breaking the 
bulb with the substance before the heating, but is un- 
necessary if the latter is enclosed in test-tube glass 
with a long capillary. The larger tube is 30-35 cm 
long and 1.2-1.5 cm inner diameter; both ends are 
drawn out, the one to fit into a tube 10 cm long and 
I-2 cm inner diameter, which is sealed to a wider 
tube, the other so that a piece of stout rubber tube will 
fit over it quite tightly. The drawn-out ends must be 
strong enough to resist the pressure during the heat- 
ing, and sufficiently thin to be readily broken after 
being scratched with a file. The substance and hydri- 
odic acid are heated at 130° during two hours, then, 
when cold, one point of the tube is fitted into the nar- 
row one mentioned. above, the wide portion of which 
passes through a triply bored cork into a wide-mouthed 
flask. Into the second opening of the cork the con- 





1 Zeisel, M. 7, 406. | 


46 RADICLES IN CARBON COMPOUNDS. 


denser fits, whilst the third contains a piece of stout 
glass rod bent to a Z form; by turning this the drawn- 
out end of the heating-tube is broken. The contents 
are transferred to the flask partly by shaking, partly 
by gently warming; the upper capillary is covered with 
a piece of rubber, the end broken, and a current of 
carbonic anhydride immediately passed through the 
apparatus. The determination then proceeds in the 
manner already described. 


3. MODIFICATION OF ZEISEL’S METHOD.! 


Instead of red phosphorus and water the potash bulbs 
contain a solution -consisting of arsenious anhydride (1 
part), potassium carbonate (I part), and water (10 
parts). The bulbs must be refilled for each determina- 
tion to prevent the apparatus becoming choked with 
precipitated anhydride, but this is compensated for by 
the fact that not the slightest reduction (blackening) of 
the silver nitrate solution takes place. The N/Io 
silver nitrate solution is made by dissolving the nitrate 
(17 grams),in water (30 cc.),and diluting to a liter with 
commercial absolute alcohol, its titer being determined 
by means of N/io potassium thiocyanate solution. 
For the alkyloxyl determination the silver solution 
(75 cc.) is acidified with a few drops of nitric acid, free 
from nitrous acid, and divided between the-two absorp- 
tion flasks. At the conclusion of the experiment the 
silver solution with the precipitate is diluted with water 
to 250 cc, cautiously shaken, filtered by means of a dry 
ribbed filter into a dry flask, and 50 cc. or 100 cc. of the 





1J. Gregor, M. 19, 116, 


~ 


METHOXYL, ETHOXYL, AND CARBOXYL. 47 


clear filtrate acidified with nitric acid, free from nitrous 
acid, treated with ferric sulphate solution, and titrated 
in the ordinary manner.! (Cf. p. 114.) 

It has been stated that this method is unreliable on 
account of the action of methylic iodide on the arsenical 
liquid* but further investigation shows that accurate re- 
sults are obtained if the arsenious solution is less con- 
centrated.$ 


METHOD FOR THE DIFFERENTIATION OF METHOXYL 
AND ETHOXYL. 


Zeisel’s method does not distinguish between me- 
thoxyl and ethoxyl; should this be necessary, the alkyl 
iodide must be prepared in quantity sufficient for its 
identification, or, if possible, Lieben’s iodoform test 
must be applied. For the differentiation of the alkyls 
the investigation of the action of phenyl isocyanate on 
the alkyloxy derivatives has been suggested.* The 
compound is heated with phenyl isocyanate, in equi- 
molecular proportion, at 150°, during several hours, in 
a sealed tube. The product is steam-distilled, and the 
volatile portion purified by recrystallization from a mix- 
ture of ether and light petroleum ; methylphenylurethane 
melts at 47°, ethylphenylurethane at 50°, and they 
can be further distinguished by analysis. 





1 Volhard, J. pr. 9, 217. Ann..190, 1. Z. anal. 13, 171; 17, 482. 
2 J. M. van Charante Rec, 21 (1902), 38. 

3 Pribram, private communication, 

* Beckmann, Ann, 292, 9, 13. 


48 RADICLES IN CARBON COMPOUNDS. 


DETERMINATION OF ETHOXYL (C,H,O-). 


The determination of ethoxyl! is carried out exactly 
in the manner described in the preceding section for 
methoxyl except that the water in the condenser and 
in the bath surrounding the potash bulbs should be 
heated at about 80°. 100 parts of silver iodide 
=+ 19.21 parts C,H,O = 12.34 parts C_H.. 

The method is also applicable to butyl and amyl 
ethers, i.e. to the determination of butoxyl C,H,O, 
and amoxyl C,H,,O.’ 


~, DETERMINATION OF CARBOXYL (CO.OH). 


The following methods are employed for the deter- 
mination of the basicity of organic acids: 
(A) Analysis of metallic salts of the acid. 
(B) Titration. 
_ (C) Etherification. 
(D) Determination of the electrolytic conductivity 
of the sodium salts. 
(E) Indirect methods: 
(1) Carbonate method. 
(2) Ammonia method. 
(3) Hydrogen sulphide method. 
(4) Iodine method. 
It is easy to decide which of these methods is the 
most suitable for any special case, but the qualitative 
differentiation between carboxyl and phenolic hydroxyl 





1 Zeisel, M. '7, 406. 
2S. Zeisel and R. Fanto, Zeit. landw. Versuchs. Wes. Oesterr. 5 
(1902), 729. Journ, Chem, Soc, 82, ii. (1902), 111, 585. 


 : 


" METHOXYL, ETHOXYL, AND CARBOXYL. 49 


frequently presents difficulties that can only be over- 
come with certainty by the preparation of the amide 
and its conversion into the nitrile. 


(A) Determination of Carboxyl by Analysis of Metallic 
Salts of the Acid. 


In many cases the number of carboxyl groups in an 
organic compound may be determined by the analysis 
of its neutral salts; of these the sz/ver salts are usually 
the most appropriate, as they are generally formed di- 
rectly without admixture of hydrogen salts, and are 
almost always anhydrous. Exceptions to this rule are, 
however, encountered; thus the silver salts of canthar- 
idinic acid,’ camphoglycuronic acid,? and metaquinal- 
dinic acid’ crystallize with one, three and four 
molecules of water respectively, and hydrogen silver 
salts, though not of frequent occurrence, are known. 
Aromatic hydroxymonocarboxylic acids containing 
two nitro-groups often give salts containing two atoms 
of silver. As examples may be mentioned 3:5-dinitro- 
hydrocumaric, 1: 3: 5-dinitroparahydroxybenzoic, and 
2 :6-dinitro-5-hydroxy-3-4-dimethylbenzoic acids. 
Many silver salts are very sensitive to light or air, and 
some, like silver oxalate® and silver lutidonemonocar- 
boxalate? are explosive; for the analysis of such the 





1 Homolka, B. 19, 1083. 

2 Schmiedeberg and Meyer, Z. physiol. Chem. 3, 433- 

3 Eckhardt, B. 22, 276. 

4 A list of them is given in Lassar-Cohn, ‘‘ Manual of Organic Chem- 
istry,”’ translated by Alex. Smith, p. 345. 

5 W. H. Perkin, Jun., Journ. Chem. Soc. 75 (1899), 176. 

6 B. 16, 1809. 

7 A. P. Sedgwick and N, Collie, Journ. Chem. Soc. 67 (1895), 407. 


50 RADICLES IN CARBON COMPOUNDS. 


compound is dissolved or suspended in water or acid, 
and treated with hydrogen sulphide or hydrochloric 
acid. Silver salts which do not explode when heated 
are usually analyzed by ignition in a porcelain crucible; 
if the residual silver contains carbon it is dissolved . 
in nitric acid, the solution diluted and filtered, and the 
silver precipitated by means of hydrochloric acid. 

Pyridine and quinoline derivatives and amino-acids 
frequently give characteristic copper and nickel salts, 
whilst, in the aliphatic series, the zivc salts may often 
be usefully employed. Sodium, potassium, calcium, 
barium, magnesium, and, less frequently, lead salts » 
are also sometimes used for the determination of 
basicity, but, as many acids do not yield well-defined 
neutral salts, and groups other than carboxyl can ex- 
change hydrogen for metal, the method has not a very 
wide application. 


(B) Titration of Acids. 


The basicity of a carboxyl derivative may often be 
determined by titration if the molecular weight of the 
compound is known; N/1o sodium hydroxide, potas- 
sium hydroxide, or barium hydroxide may be used for 
the titration in aqueous solution, or, in the case of the 
first two, in alcoholic solution. N/2 ammonium 
hydroxide has also been employed.! The acids used 
are generally hydrochloric or sulphuric, but the latter 
is unsuited for work with alcoholic solutions, as the 
precipitation of insoluble sulphates prevents a correct 
observation of the end reaction. ‘The liquid, alcohol, 
ether, etc., in which the compound under examination 





1 Haitinger and Lieben, M. 6, 292. 


~ 


METHOXYL, ETHOXYL, AND CARBOXYL. 51 


is dissolved, must either be free from acids or must pre- 
viously be exactly neutralized by means of N/10 alkali. 
Phenolphthalein, methyl orange, rosolic acid, cur- 
cumin, or litmus, are usually employed as indicators, 
the first two more frequently than the others. Ifthe 
liquid is dark colored the use of ‘‘ alkali blue’’ is often 
convenient, and attention must always be paid to the 
possible presence of carbonic anhydride. The be- 
haviour of various acids, hydroxy acids, phenols, and 
their substitution products with helianthin, phenol- 
phthalin, and Poirrier’s blue has been studied. A 
somewhat curious and interesting attempt has been 
made to determine the neutrality by taste.’ 

Certain lactones can be titrated with alkali although 
they are insoluble in sodium hydrogen carbonate.? a- 
Dibenzoylsuccinic lactone may be easily titrated, in 
alcoholic solution, with N alkali by the use of phenol 
phthalein.4 Hydroresorcinol behaves in a similar 
manner.® 


(C) Esterification. 


In very many cases carboxylic and phenolic hydrogen 
may be differentiated by the esterification of the com- 
pound with alcohol and hydrogen chloride. It has, 
however, been shown® that acids with the group 





1H. Imbert and A, Astruc, C. r. 130 (1900), 35. Journ. Chem. Soc. 
78 (1900), i. 226. 

2 T. W. Richards, Am. Chem. Journ., 20, 125. 

3H. L. Fulda, M. 20 (1899), 700. 

4L. Knorr, Ann. 293 (1897), 87. 

5 R. v. Schelling, /é7d. 308 (1899), 185. 

6'V. Meyer and others. Many papers appeared on the subject 
beginning B. 27, 510, and ending 29, 2569. 


52 RADICLES IN CARBON COMPOUNDS. 


C.COOH 
voM (t and t’ = tertiary carbon atom) do not yield 
oo 


t t 


esters with alcohol and hydrogen chloride if both the 
carbon atoms marked t are linked to Cl, Br, I, or NO,, 
while the groups of smaller mass F, CH,, OH in the 
same positions greatly retard, but do not entirely pre- 
vent, esterification. On the other hand, certain phe- 
nols such as phloroglucinol,' which gives a diether and 
triether®, hydroxyanthracene (anthrol), and a@- and f- 
naphthol’, yield ethers when treated with hydrogen 
chloride and alcohol. The esterification is most con- 
veniently carried out by boiling the substance for 3—5 
hours in a reflux apparatus with a large excess of ab- 
solute alcohol containing 3-5 per cent of hydrogen 
chloride or sulphuric acid.4 Occasionally alcohol of 
95 per cent may be employed if more sulphuric acid is 
used.5 Some substances form additive compounds 
with alcohol and hydrogen chloride. This, as also 
the contamination of the ester by traces of chlorine 
derivatives, which can only be removed with difficulty, 
may lead to confusion. Certain compounds prepared 
from carbamide and ethereal dihydroxysuccinates con- 
tain OH groups; they are not acids but they readily 
etherify with hydrogen chloride and ethylic alcohol.’ 





1B. 17, 2106; 21, 603. 

2 J. Herzig and H. Kaserer M. 21 (1900), 993. 

3 Liebermann and Hagen, /ézd. 15, 1427. 

4 E. Fischer and A. Speier, B. 28, 3252. 

5 Bishop Tingle and A, Tingle, Am. Chem. Journ, 21, 243. 

6 Freund, B. 32, 171. 

7H. Gersenheimer and R. Anschiitz, Ann. 306 (1899), 41, 54. 


@. 


METHOXYL, ETHOXYL, AND CARBOXYL. 53 


The esters obtained by acid or alkaline esterification 
are, in general, distinguished from the phenolic ethers 
by the ease with which aqueous or alcoholic alkalis 
hydrolyse them, but exceptions are known since trini- 
tromethoxybenzene (methyl picrate) when boiled 
with concentrated potassium hydroxide yields methyl 
alcohol and potassium picrate,’ and methoxyanthracene 
(methyl anthranol) is also decomposed by boiling with 
alcoholic potash.” Dimethyl o-nitrocumarate yields 
the monoether when boiled with dilute alkali, the acid 
is only formed by prolonged heating with concen- 
trated alkali in excess.? The silver salts of hydrox- 
amide and phenylhydroxamide yield ethylic esters 
R.COH:N.OC,H, which behave as monobasic acids 
when titrated with caustic alkalis.‘ 

The composition of esters is determined by ele- 
mentary analysis, and the alkyloxy groups by the 
methods described in the earlier portion of this chapter. 


(Chop: -382) 
(D) Determination of the Basicity of Acids by means 


of the Electrolytic Conductivity of the Sodium 
Salts. 


It has been shown that the degree of electrolytic 
conductivity of the sodium salt is a certain indication 
of the basicity of the corresponding acid.5 The method 
is of very general application, since insoluble acids 





1 Ann. 174, 259. 

2 Liebermann and Hagen, B. 15, 1427. 

3 W. v. Miller and F. Knikelin, /ézd¢. 22 (1889), 1710. 

4R. H. Pickard, C. Allen, W. A. Bowdler and W. Carter, Journ. 
Chem. Soc. 81 (1902), 1565. 

5 Ostwald, Z 2, 901; 1, 74. Valden, /é7d. 1, 529; 2, 49. 


54 RADICLES IN CARBON COMPOUNDS. 


usually yield sodium salts which dissolve in water, but 
it fails in the case of acids which are so feeble that their 
sodium salts are hydrolysed by water sufficiently to 
impart an alkaline reaction to the solution. The fol- 
lowing apparatus is required for the determination: 

(1) A small zxduction coil (J, Fig. 8), such as is em- 
ployed for medicinal purposes, and which requires only 
* one or two cells for prolonged use. The spring of the. 
interrupter must vibrate rapidly so as to produce a high- 
pitched sound in the telephone, as this is more easily 
heard than a deeper tone. 

(2) A bridge consisting of a scale 100cm. in length 
divided into millimeters; along it stretches a wire pro- 
vided with a sliding contact. The wire is of platinum, 
German silver, platinoid, or manganin, the last is the 
best on account of its low temperature coefficient. 
The wire must be calibrated.'. For high resistances 
(1,000-200,000 Ohms) the special form of resistance 
coil described by Chaperon* should be used instead 
of the wire. 

(3) Arheostat for adjusting the resistance (W, Fig. 8), 

(4) A resistance cell for the electrolyte (E, Fig. 8). 
Kohlrausch’s form (Fig. 6) is used for low resist- 
ances, whilst that of Arrhenius (Fig. 7) is employed 
for dilute solutions where the resistance is high. The 
electrodes must be platinised by filling the vessel with 
a dilute solution of hydrochloroplatinic acid and passing 





1 Strouhal and Barus, Wied. Ann, 10, 326. The method is also 
described by Jones, ‘‘ Freezing-point, Boiling-point, and Conductivity 
Methods,” Chem. Pub. Co., 1897. 

2C. r. 108 (1894), 799. 

3 E. Cohen, L. 25 (1898), 16. 


~™~ 


METHOXYL, ETHCXYL, AND CARBOXYL. 55 


a current of 4—5 volts. The direction of the current 
is changed occasion- 
ally: and. the. -électro= 
lysis continued until 
bot. c1ectrodes. “are 
completely | covered 
with platinum black; 
this requires only a 
short time. The pla- 
tinum chloride in the Fic. 6, 
cell is now replaced , 

by sodium hydroxide 

solution, the electrolysis continued for a few mo- 
ments, the electrodes thoroughly and carefully 
washed with hydrochloric acid, and finally with water. 
The sodium hydroxide removes all chlorine, which is 
otherwise very obstinately retained by the platinum. 
The use of Lummer and Kurlbaum’s solution for plati- 
nising is highly recommended, as the tone minima are 
much more distinct." The solution consists of plati- 
num chloride (1 part), lead acetate (0.008 part), and 
water (30 parts); it is electrolysed with a current 
density of 0.03 ampéres per sq. cm, the direction of 
the current being frequently changed and continued 
until each electrode has been the cathode during at 
least fifteen minutes. 

(5) A telephone. Ostwald states that the most sensi- 
tive ones are made by Ericsson of Stockholm, but for 
ordinary purposes a Bell instrument is sufficiently good. 
In using it the unoccupied ear may be closed with cot- 
ton to exclude external sounds. 




















FiG:-7- 





1 Kohlrausch, Wied. Ann. 1897, p. 315; E. Cohen, Z. 25, 1611. 


56 RADICLES IN CARBON COMPOUNDS. 


(6) A water bath with stirrer and thermometer, or 
a thermostat.' 

The apparatus is arranged in the form of Kirchhoff’s 
modification of the Wheatstone bridge (Fig. 8), the con- 
nections being made with stout copper wire. © The in- 
duction coil is enclosed in a sound tight case, or is 
placed in another room. If 
determinations of solutions 
of a substance at different 
concentrations are to be 
made, the solution is most 
conveniently prepared in 

Fic. 8. the resistance cell itself, 
portions are then withdrawn by means of an accu- 
rately calibrated pipette, and the desired volume 
of water added, which has previously been brought 
to the necessary temperature in the thermostat. As 
a rule the telephone does not give an absolutely 
sharp minimum at any given point, but it is easy 
to find two limits beyond either of which the tone 
rises; these are usually separated by an interval of 
0.5—2 mm, and the required position is taken as mid- 
way between them. A little experience enables the . 
observer to determine the conductivity with an accu- 
racy of 0.1 per cent. If the tone minimum becomes 
indistinct the electrodes must be replatinised. The 
conductivity is calculated from the measurements by 








means of the formula “ = b= — where 





1 Ostwald, Z. 2, 564, where also a good description of the other parts 
of the apparatus is given, 


™~ 


METHOXYL, ETHOXYL, AND CARBOXYL. 57 


wt = the molecular conductivity ; 

v = the volume in liters of the solution which contains 
a gram molecule of the electrolyte; 

w — the adjusting resistance; 

a = the length of wire to the left of the sliding con- 
tact (Fig. 8); 

6 = that to the right of the contact (Fig. 8) 

k = the resistance of the cell. 

The value of £ is determined by measuring the con- 
ductivity of N/s50 solution of potassium chloride, for | 
which Kohlrausch found the values: 

(= 122-30 io 
pi = 126.7 at25-. 
Other solutions may also be used.' The value : 


for a wire 1000 mm in length has been calculated by 
Obach and an abbreviated table of the results is given 
in the appendix. The conductivity of the water em- 
ployed, which should be as highly purified from dis- 
solved substances as possible, is determined in the 
same manner as that of the solution, the value for each 
liter (v) is calculated according to the formula, and 
subtracted from the uncorrected value of mw. For 
basicity determinations the conductivity is usually de- 
termined at concentrations of one gram molecule in 32 
and 1024 liters respectively. The mean difference J 
between these values is as follows: 


Monobasic acids <2. .<4) = 1004 =I XK 10.4 
Dibasic Se PO Oe OC re 
Tribasic saa rea 4 ioe 8 fy rete bp Gan 0 
Letrabasie®: “(ey = Ait AO 


Pentabasic: 66 09206 oO he BO 
1 Wiedemann and Ebert, Physik. Praktikum, p. 389. 





58 RADICLES IN CARBON COMPOUNDS. 


A method has been described! for determining the 
basicity of acids based on the alterations which they ex- 
hibit in electrolytic conductivity on the addition of alkali. 

Instead of the telephone and induction coil, a double 
commititator and a galvanometer may be used to de- 
termine the electrolytic conductivity, the commutating 
apparatus, termed a secohmmeter, is so arranged that 
one commutator is included in the battery circuit and 
the other in that of the galvanometer; on rotating, the 
current is reversed in the liquid so frequently that polari- 
zation is annulled and the galvanometer commuted.* 

A neat form of apparatus*®, much smaller than Kohl- 
rausch’s, consists of an ebonite cup and rod fitted with 
platinum electrodes prepared in the usual manner. 
The rod can be moved vertically over the cup by 
means of micrometer screws, and the distance between 
the electrodes read off on a divided scale by a vernier. 
Quantities of solutions as small as 3 cc may be employed. 


(E) Indirect Methods for the Determination of the 
Basicity of Acids. 


These methods may be divided into four classes ac- 
cording to the nature of the substance liberated by the 
acid: 

(1) Carbonate method. 

(2) Ammonia method. 

(3) Hydrogen sulphide method. 

(4) lodine-oxygen method. 





1D. Berthelot, C. r. 112, 287. 

* Cahart and Patterson, ‘‘ Electrical Measurements,” p. 109. 

3 R. Goldschmidt and A. Reychler, Bull. 19 (1898), iii. 675; Journ. 
Chem. Soc. 76 (1899), ii. 463. 


~ 


METHOXYL, ETHOXYL, AND CARBOXYL. 59 


(1) Carbonate Method.—The substance (0.5—I gram) 
is dissolved in water in a flask closed by a rubber stop- 
per with three holes. In one hole a condensing tube is 
fitted, which, at the lower end, is flush with the stop- 
per while the upper end is connected with an dbsorp- 
tion apparatus consisting of two calcium chloride tubes 
and potash bulbs. Through the second hole a tube 
passes to the bottom of the flask, the end being drawn 
out and bent upwards; by means of this tube a current 
of air, free from carbonic anhydride, is passed. The 
third hole of the flask is closed with a small dropping 
funnel, the end of which also is drawn out and bent 
upwards, being run below the liquid in the flask. The 
solution of the acid. is gently boiled, and barium car- 
bonate, in the form of a thin paste, is added in small 
quantities by means of the funnel. When the operation 
is completed the apparatus is allowed to cool in a cur- 
rent of purified air, again boiled, cooled, and the ab- 
sorption bulbs weighed.!. A similar method, based on 
the decomposition of sodium hydrogen carbonate, has 
also been described. 

(2) Ammonia Method.—The acid (about I gram) is 
dissolved in excess of alcoholic potassium hydroxide, 
and made up to 250 cc with alcohol of the same 
strength (93 per cent). The excess of alkali is neu- 
tralized by carbonic anhydride, the precipitated car- 
bonate and bicarbonate filtered off and washed with 50 
cc of alcohol (98 per cent). The alcohol is removed 
from the filtrate and washings by distillation, and the 
residue boiled with 100 cc of ammonium chloride solu- 





1 Goldschmiedt and Hemmelmayr, M. 14, 210-.-——-== 
2 Vohl B. 10, 1807. C. Jehn, /éid. 10, 2 A BRA 
oO 





60 RADICLES IN CARBON COMPOUNDS. 


tion (10 per cent). The potassium salt of the acid de- 
composes the ammonium chloride, and the liberated 
ammonia is determined in the usual manner. The 
amount of alkali carbonate dissolved by 100 cc of 
alcohol (93 per cent) is equivalent to 0.34 cc of nor- 
mal acid; a correction for this must be applied and also 
one for the ammonium chloride hydrolysed by the 
water; this is determined by a blank experiment, 100 
cc of the solution being boiled during the same length 
of time, I—2 hours, as in the actual determination. ! 

The method gives good results with the feebler fatty 
acids, and is especially useful when the dark color of 
the solution prevents direct titration. 

(3) Hydrogen Sulphide Method.* Compounds con- 
taining carboxyl liberate hydrogen sulphide from cer- 
tain metallo-hydrogen sulphides when allowed to react 
in an atmosphere of hydrogen sulphide, according to 
the equation: 


NaSH + R.COOH + xH,S»-RCOONa- 
+H S-+ xH,S 


two volumes of hydrogen sulphide being liberated for 
each volume of hydrogen, replaceable by metal, in the 
original compound. Hydroxyl hydrogen in phenols, 
alcohols, and hydroxy-acids does not react with the 
metallo-hydrogen sulphides. 


Preparation of the Solution. 


The majority of alkali salts are sparingly soluble in 
solutions of the hydrosulphides; hence the solution of 





1P. C. Mcllhiney, J. Am. 16, 408. 
2 F. Fuchs, M. 9, 1142, 1153; 11, 363. 


~ 


METHOXYL, ETHOXYL, AND CARBOXYL. 61 


the latter must not be so concentrated as to hinder the 
reaction from being rapidly completed. Potassium 
hydroxide solution, not exceeding Io per cent, is boiled 
with baryta water in excess, the flask closed, and the 
liquid allowed to cool and deposit barium carbonate. 
The clear solution is now poured into the vessel to be 
used for the analysis, and saturated with hydrogen 
sulphide. 


Method of Analysts. 


The evolved hydrogen sulphide may be determined: 

(a) volumetrically, 

(6) by tetration. 

The former method is the easier, and is therefore 
generally employed. 


(a) Volumetric Determination. 


This method is based on the same principle as Victor 
Meyer’s vapor density determination. The apparatus, 
Fig. 9, consists of a long-necked flask A, made of thick 
glass; it is fitted with a rubber stopper c through 
which the delivery tube B passes, this is wide at one 
end but terminates in a capillary at the other. The 
second hole of the stopper is closed by means of a 
glass rod from which the vessel containing the sub- 
stance is suspended. Previous to the determination 
the greater portion of the flask is filled with hydro- 
gen sulphide, but the upper portion of the neck and 
the delivery tube contain air which is expelled by the 
evolved hydrogen sulphide and collected over water 
in a graduated tube. The substance under examina- 


62 RADICLES IN CARBON COMPOUNDS. 


tion is dried, finely powdered, and about 0.5 gram 
weighed into the 
small vessel, the 
glass rod being 
pressed into the 
rubber stopper as 
far as the mark 1, 
the vessel fitted 
on to it by means 
of the stopper, 
which, with the 
delivery tube, is 
pressed air-tight 
into the flask. 
The apparatus is 
allowed to re- 
main for a few moments to equalize the temperature, 
then the capillary end of the delivery-tube is dipped 
into water below the open end of the gas-measuring 
vessel, and the vessel with the substance dropped into 
the sulphide solution by pushing in the rod to the 
mark 2, care being taken not to alter the position of 
the stopper itself. The evolution of hydrogen sulphide 
ceases after a few minutes. The same solution may 
be employed for a second or third determination, but 
each time the delivery-tube must be previously filled 
with dry air. The weight of carboxyl hydrogen G is 
calculated from the results by the formula: 
G ost V(b— W) 
760(1 + 0.003662) 
V.(6—w).0.00000005 895 
es I + 0.003662 f 











.0.0000896 








~ 


METHOXYL, ETHOXYL, AND CARBOXYL. 63 


where V7 = the observed volume of air displaced in 
cc, 6= the height of the barometer, and w the tension 
of aqueous vapor at the observed temperature 7. 


(6) Titration Method. 


The apparatus employed consists of a short-necked 
.flask A, Fig. 10, fitted with a rubber stopper and glass 
rod exactly as used in the 
preceding method, but the 
delivery-tube is short in order 
to expedite the expulsion of 
air. Before the stopper, with 
the substance adjusted in the Ly 
manner described above, is in- = 
serted into the flask, tartaric 
acid or oxalic acid (about 0.25 gram) is dropped into 
the potassium hydrogen sulphide solution and the stop- 
per immediately inserted air-tight as shown. As soon 
as the evolution of gas ceases the beaker represented in 
the figure is replaced by a smaller one containing con- 
centrated potassium hydroxide solution. Some of this 
rises in the tube on account of the absorption of the 
gas, but the error so introduced compensates itself at 
the end of the experiment. As soon as the beaker of 
alkali has been put into position, the substance is 
dropped into the sulphide solution with the same pre- 
cautions as observed in the preceding method; after 
the cession of the gas evolution, which continues dur- 
ing 1-5 minutes, the pressure is adjusted by lowering 
the beaker, the contents are poured into a large flask, 
and the beaker and evolution tube washed. The alkali 
and washings are diluted to about 500 cc, neutralized 











64 RADICLES IN CARBON COMPOUNDS. 


with acetic acid, and titrated with iodine solution in 
presence of starch. Since 
eee epee a oe 

the iodine required, divided by 2 x 126.5, gives the 
weight of the replaceable hydrogen. The error due 
to the insertion of the glass rod from mark I to 2 may | 
be determined by means of a blank experiment, but 
it is so small as to be usually negligible. More re- 
cently the action of substituted phenols, etc., on alkali 
hydrogen sulphides has been investigated’ with the 
following results: 

(1) Haloid substituted phenols with one hydroxyl 
group are without action on the sulphides, but if ¢zwo 
hydroxyl groups are present ome reacts. 

(2) Only the paramononitro-phenols react. 

(3) Under certain conditions the presence of car- 
boxyl groups causes the phenolic hydroxyl to decom- 
pose the sulphides. 

(4) In general lactones do not react, but lactone- 
acids may suffer partial resolution.? 

With the above exceptions the method provides a 
ready means of differentiating carboxylic hydrogen 
from phenolic or alcoholic, a distinction which the two 
preceding methods do not furnish with certainty. 

(4) Lodine-oxygen Method.* This depends on the 
fact that even feeble organic acids liberate iodine from 
potassium iodide and potassium iodate in accordance 
with the equation: 


6R.COOH+sKI+KI0,>6R.COOK + 3I,-+ 3H,O. 





* 1 Fuchs, M. 11, 363. 2 H. Meyer, /éid. 19, 715. 
3’ Baumann and Kux, Z, Anal. Ch, 32, 129. 


~ 


METHOXYL, ETHOXYL, AND CARBOXYL. 65 


The liberated iodine, in presence of alkali, evolves” 
oxygen from hydrogen peroxide: 


I,+2KOH-—-KOI-+KI-+H,0O and 
KOI-+-H,0,-KI+-H,0O+0,. 

The oxygen may be measured in a modified Wagner & 
Knop’s azotometer,! or in any other convenient vessel. 

The apparatus consists of an evolution flask, with a 
small cylinder of about 20 cc capacity fused to the 
middle of the bottom inside, and a large glass cylinder 
with two communicating burettes and a thermometer, 
fastened to the interior of the cover. The cylinder and 
burettes are filled with water, the latter by connecting 
them with a flask from which water is forced by air 
pressure from a hand blower, the connecting tube being 
provided, if needful, with a stop-cock. The evolution 
flask is closed by means of a rubber stopper carrying 
a tube with a stop-cock which is connected with the 
graduated burette below the stop-cock in which the 
latter terminates, and which is used for adjusting the 
pressure. The temperature of the evolution flask is 
equalized, before and after the determination, by placing 
it in water of the same temperature as that in the large 
cylinder enclosing the burettes. The following rea- 
gents are required: 


(1) Potassium iodide ) 

(2) ‘“¢ iodate } 

(3) Hydrogen peroxide 2—3 per cent solution. 

(4) Aqueous potassium hydroxide solution (1 : I). 

(5) Distilled water, recently boiled and free from 
carbonic anhydride. 


absolutely free from acid. 





1Z. Anal. Ch. 13, 389. 


66 RADICLES IN CARBON COMPOUNDS. 


The determination is carried out in the following 
manner: The acid (0.1-0.2 gram) is mixed with finely 
divided potassium iodate (about 0.2 gram), potassium 
iodide (2 grams), and water (40 cc) ina bottle provided 
with’ a well-fitting stopper, and allowed to remain at 
the ordinary temperature during twelve hours, or at 
70°—80° during a half hour, until the iodine is com- 
pletely precipitated. The solution is nowtransferred to 
the outer portion of the evolution flask, the bottle being 
washed with not more than 10 cc of water. Into the 
inner cylinder of the evolution flask is poured, by 
means of a funnel, a mixture consisting of hydrogen 
peroxide (2 cc) and potash solution (4 cc), made im- 
mediately before use, and cooled to the ordinary tem- 
perature. The evolution flask is now closed with its 
stopper and allowed to stand in water during ten min- 
utes, the stopcock of the burette being opened to equal- 
ize the pressure; at the end of this time it is closed, 
the level adjusted to the zero mark, and if, after five 
minutes, no change takes place the experiment is pro- 
ceeded with, otherwise the cooling is continued during 
another five minutes. When equilibrium is established 
30-40 cc of water are run from the burette in order to 
reduce the pressure, the evolution flask is removed from 
the cooling vessel by means of a cloth and rotated so 
that the liquids at first circulate without mixing and 
are then suddenly brought into contact. The shaking 
is continued vigorously for a short time and the flask 
then returned to the cooling vessel. The evolution of 
oxygen begins at once, and is completed in a few sec- 





1 Baumann, Z, f. ang. Ch. 1891, p. 328. 


~ 


METHOXYL, ETHOXYL, AND CARBOXYL. 67 


onds; after about ten minutes the pressure in the two 
burettes is adjusted and the volume read; the number 
of cc of gas, multiplied by the value in the table! in the 
appendix corresponding to the pressure and tempera- 
ture, gives directly the weight of carboxylic hydrogen. 
An todometric method for the determination of acids 
has also been described; for details, the original paper 
should be consulted.! 





*M. Gréger, fda, 1890, pp. 353, 385. 


CHAPTER III. 
ej 
DETERMINATION OF CARBONYL (CO). 


The presence of the carbonyl group in aldehydes, 
ketones, etc., is recognized by the preparation of de- 
rivatives of the following compounds: 


(1) Phenylhydrazine and its substitution products; 

(2) Hydroxylamine ; 

(3) Semicarbazine ; 

(4) Thiosemicarbazine ; 

(5) Semioxamazine; 

(6) Aminoguanidine; 

(7) Paraminodimethylaniline; 

(8) Barium salts of- aromatic aminocarboxylic or 
aminosulphonic acids; 

(9) Miscellaneous derivatives. 


(1) CARBONYL DETERMINATION BY MEANS OF 
PHENYLHYDRAZINE. 


The method is divisible as follows: 


(A) Preparation of phenylhydrazones from phenyl- 
hydrazine. 
(B) Preparation of substituted hydrozones. 


(C) lLndirect Method. 
68 


™ 


DETERMINATION OF CARBONYL. 69 


(A) Preparation of Phenylhydrazones.’ 


Carbonyl compounds combine with phenylhydrazine 
forming water and phenylhydrazones, 


CH NH-.N:CRE: 


diphenylhydrazones, with the hydrazine groups linked 
to neighboring carbon atoms, are termed osazones. 
The reaction usually takes place most readily in dilute 
acetic acid solution, often at.the ordinary temperature, 
almost always by heating on the water-bath. Fre- 
quently it is advisable to allow the reaction to proceed 
at the ordinary temperature in presence of concentrated 
acetic acid, which acts as a dehydrating agent and in 
which the phenylhydrazones, as a class, are sparingly 
soluble.?, E. Fischer dissolves or suspends the sub- 
stance in water or alcohol, and adds, in excess, a mix- 
ture of phenylhydrazine hydrochloride (1 part) and 
crystallized sodium acetate (1.5 parts) dissolved in 
water (8-10 parts).. Free mineral acids must be neu- 
tralized by means of sodium hydroxide or sodium car- 
bonate, as their presence hinders the reaction; the 
presence of nitrous acid is particularly hurtful and it 
must be removed by means of carbamide, as otherwise 
it reacts with the phenylhydrazine and forms diazoben- 
zene imide and other oily products. Confusion may 
also be caused by the production of acetylphenylhydra- 
zine from the dilute acetic acid.’ 

The phenylhydrazones gradually separate from the 
solution of their components in an ‘oily or crystalline 





1 E. Fischer, B. 16, 661, 2241, foot-note; 17, 572; 22, 90. 
2 Overton, B. 26, 20. 5 Anderlini, /é7d, 24, 1993, foot-note. 


7O RADICLES IN CARBON COMPOUNDS. 


form, and, in the latter case, are purified by recrystal- 
lization from water, alcohol, or benzene. 

It is often desirable to heat the compound under in- 
vestigation with free phenylhydrazine, and increased 
pressure may be used if there is no danger of phenyl- 
hydrazides being formed.’ The product is poured into 
water, the phenylhydrazone removed by filtration, 
washed with dilute hydrochloric acid to free it from 
excess of phenylhydrazine, and recrystallized; in some 
cases glycerol is employed for washing, the last por- 
tions of it being removed by water.? Aliphatic ketones 
react readily in ethereal solution, and the water which 
is produced may be absorbed by recently ignited po- 
tassium carbonate or calcium chloride. In the case of 
ketophenols or ketoalcohols the hydroxyl group should 
be acetylated before treatment with phenylhydrazine; 
acids are usually used in the form of esters, but the 
sodium salt is sometimes employed’; the condensa- 
tion is occasionally promoted by the addition of a min- 
eral acid.4| Hydrazones may also be prepared from 
oximes.> The carbonyl group in many lactones and 
acid anhydrides, although it does not react with 
hydroxylamine, yields phenylhydrazides (additive com- 
pounds), or, at high temperatures, condensation pro- 
ducts. Hydrazine also yields additive compounds 
with some aromatic lactones. Hydroquinonetetracar- 





1M. 14, 395. 2 Thoms, B. 29, 2988. 

3 Bamberger, /d7d. 19, 1430. * Elbers, Ann, 227, 353. 

5 Just, B. 19, 1205. v. Pechmann, /d7d. 20, 2543, foot-note, 

6 W. Wislicenus, /é¢d. 20 (1887), 401. E, Fischer and F, Passmore, 
Ibid, 22 (1899), 2733. L. Gattermann and R. Ganzert, /dzd, 32 (1899), 
1133. J. Wedel, /dzd. 33 (1900), 1766. R. Meyer and E, Saul, /éid, 
26 (1893), 1271. Ephraim, /éid. 26,1376. v, Meyer and Miinchmeyer, 


“= 


DETERMINATION OF CARBONYL. 7s 


boxylic anhydride forms a compound with phenyl- 
hydrazine, which is not a hydrazide but is similar to 
the corresponding derivative of phthalic anhydride.! 
Many quinones, such as anthraquinone, do not react 
with phenylhydrazine or only with one molecular pro- 
portion, as in the case of naphthoquinone and phenan- 
thraquinone, whilst some, such as benzoquinone and 
toluquinone, oxidize it to benzene.* Ortho-disubsti- 
tuted ketones frequently do not react with phenyl- 
hydrazine,* and certain unsaturated ketoalcohols, such 
as ethylic acetoacetate ‘ and ethylic camphoroxalate,® 
yield monophenylhydrazides, the ketonic group being 
unaffected. Hydroxyketones and aldehydes of the 
aliphatic series yield phenylosazones, a portion of the 
phenylhydrazine being simultaneously reduced to ani- 
line and ammonia.°® 

Osazones are often most readily purified by solution 
in pyridine, or a mixture of pyridine and one of the 
ordinary solvents. As there is a great tendency for 
the pure pyridine to form supersaturated solutions it is 
often convenient to precipitate the osazone from con- 
centrated solution in pyridine by the addition of a neu- 
tralsolvent. The solubility of the osazones in pyridine 
is almost the same as that of the parent carbohydrate.’ 





Loid, 19 (1886), 1706, 2132. Hemmelmayr, M. 13, 669; 14, 398. 
Holle, J. pr..33; 99: 

1J.U Nef, Ann. 258 (1890), 283. 2D. Di 5 30: 

3 Baum, B. 28, 3209. v. Meyer, /ézd. 29, 830, 836. 

4J. U. Nef, Ann. 266, 52. 

5 Bishop Tingle, Am, Chem, Journ. 20, 339. A. Tingle and Bishop 
Tingle, /6z7, 21, 258. 

6 KE. Fischer and Tafel, B. 20, 3386. 

7C, Neuberg, Jdzd. 32 (1899), 3384. 


72 RADICLES IN CARBON COMPOUNDS. 


Aliphatic aldehydes react quite rapidly with phenyl- 
hydrazine hydrochloride. Aliphatic ketones behave in 
the same manner towards the acetate, but react slowly, 
or not at all,with the hydrochloride. On this fact a 
method for their separation has been based. (Cf. p. 84).! 

A method has been described for the purification of 
commercial phenylhydrazine.’ 


(B) Preparation of Substituted Hydrazones. 


The chief substitution product of phenylhydrazine 
which has hitherto been employed for the preparation 
of phenylhydrazones is the parabromo-derivative. 

Preparation of Parabromophenylhydrazine.* Phenyl- 
hydrazine (20 grams) is poured into hydrochloric acid 
(200 grams, sp. gr. = I.19) and the precipitated salt 
uniformly distributed throughout the liquid, which is 
cooled to 0°; bromine (22.5 grams) is now dropped 
in, the addition occupying 10-15 minutes, the liquid 
being well shaken during this time. After remaining 
during twenty-four hours the precipitate is removed, 
washed with a little cold hydrochloric acid, dissolved 
in water, and treated with sodium hydroxide in excess. 
The base separates in flocculent crystals which are ex- 
tracted with ether, the ether evaporated, and the resi- 
due recrystallized from water. The hydrochloric acid 
mother liquor contains bromodiazobenzene chloride, 
which is reduced by the addition of stannous chloride 
(60 grams); the precipitate is separated, washed with 
concentrated hydrochloric acid, and treated with water 
and alkali, the base being collected and purified in the 





1 A. Michael, J. pr. 45 [2], 588 
2 B. Overton, B. 26, I9. 3 Michaelis, /id. 26, 2190, 


~ 


DETERMINATION OF CARBONYL. 73 


manner described above. The yield is 80 per cent. 
Bromophenylhydrazine requires to be protected from 
light and air; it should be kept in the dark in well- 
stoppered colored bottles from which the air has been 
displaced by carbonic anhydride or coal-gas. In these 
circumstances, if the compound has been highly puri- 
fied and dried, it may be retained for years without 
change; colored specimens may be readily purified by 
recrystallization from water, to which a few drops of 
sodium hydroxide should be added. The pure com- 
pound melts at 107°—109°, the acetyl derivative at 170°.! 


Substituted Phenylhydrazones. 


Parabromophenylhydrazine is well adapted for the 
identification of certain sugars, such as arabinose,*? and 
has also been used in the investigation of ionone and 
irone;* it is generally employed in acetic acid solution, 
care being taken to prevent the liquid from boiling, 
as, in these circumstances, acetyl parabromophenyl- 
hydrazine is formed.‘ 

Paranitrophenylhydrazine, prepared from _ parani- 
traniline by means of the diazo-reaction also gives well 
defined condensation products with many aldehydes and 
ketones which serve for their identification better than 
the parabromophenylhydrazones and semicarbazones. 
The reaction usually proceeds in aqueous solution with 
the hydrochloride, but the free base in alcohol or acetic 
acid may be employed.* 





1 Tiemann and Kriger, 2 E. Fischer, B. 24, 4221, foot-note. 

3 Tiemann and Kriger, /é7d. 28, 1755. 4 Jétd. 26, 2199. 

* E. Bamberger & Kraus, /é7d, 29 (1896), 1834, Bamberger, /dzd. 32 
(1899), 1806. E. Hyde, Zid, 32, 1810; F. Fust, /éid, 33 (1900), 2098. 


~ 


74 RADICLES IN CARBON COMPOUNDS. 


B-Naphthylhydrazine,’ which, like the a@-deriva- 
tive, decomposes on exposure to light, especially in 
presence of moisture, Jdenzylphenylhydrazine,* and 
methylphenylhydrazine* are all well adapted for the 
separation and identification of sugars. Methylphenyl- 
hydrazine only yields osazones with the ketoses. Oily 
phenylhydrazones of keto-bases sometimes yield crys- 
talline salts.4 

In addition the following substituted phenylhydra- 
zines have been used for the production of phenyl- 
hydrazones: adzbromo-, symmetrical tribromo-, tetra- 
bromo-, parachloro-,. partodo-, and metaditodo-,* whilst 
some derivatives of diphenylhydrazine have also been 
described. ® 


(C) Indirect Method.’ 


This method depends on allowing the aldehyde or 
ketone to react with excess of phenylhydrazine; the 
excess, together with any hydrazide, is then oxidized 
by means of boiling Fehling’s solution, the liberated 
nitrogen being collected; phenylhydrazones are not 
decomposed by this treatment. 

The reagents required are as follows: 

Fehling’s solution made by mixing equal volumes of 





1 A, Hilger and S. Rothenfusser, B. 35 (1902), 1841. 

2 L. de Bruyn and A. van Ekenstein Rec. 15, 97, 227. O. Ruff and 
G, Ollendorff, B. 32 (1899), 3234. 

3 C, Neuberg, /éid. 35 (1902), 2626, 

*M. Scholz, /ézd. 30 (1897), 2298. 

5 A. Neufeld, Ann, 248, 93. 

6 R, Overton, B. 26, 10; C. Neuberg, /did. 33 (1900), 2245. 

1H. Strache, M. 12, 514; 13, 299, Benedikt and Strache, /éid. 14, 
270, 


~ 


DETERMINATION OF CARBONYL. 75 


copper sulphate solution (70 grams CuSO,.5H,O in 1 


liter of water) and alkaline solution of sodium potassium 
tartrate (350 grams of the tartrate, and 260 grams 


potassium hydroxide in 1 liter of water). 

Sodium acetate (10 per cent solution). 

Phenylhydrazine hydrochloride (5 per cent solution.) 
The analysis is made by mixing the compound under 
examination (0.I—O.5 gram) with an accurately meas- 
ured quantity of the phenylhydrazine hydrochloride 
solution (1 part) and the sodium acetate solution (14 
parts) in a 100 cc measuring flask. The phenylhydra- 
zine hydrochloride is taken, if possible, in quantity 
sufficient to yield 15—30 cc nitrogen. Water is now 
added to the mixture in the flask so as to make the 
volume about 50 cc, and the liquid is heated on the 
water-bath during 15-30 minutes; it is then cooled, 
diluted to the mark, well shaken, 50 cc transferred to 
the dropping funnel T, Fig. 11, and the determination 











conducted in the manner described below. The flask 
A has a capacity of 750-1000 cc, and contains 200 cc 
of Fehling’s solution, which is boiled while a rapid 


76 RADICLES IN CARBON COMPOUNDS. 


current of steam is blown in from the flask B. The 
tubes D and X must be flush with the rubber stoppers 
so as to promote the removal of air. The tube R is in 
two pieces, joined by the rubber tube X,, its lower end 
is covered with a piece of rubber tube #,and dips be- 
low water inthe dish W. The current of steam is con- 
tinued until the bubbles of gas collected are very small, 
it is impossible, in a reasonable time, to remove all the 
air and a blank determination of the phenylhydrazine 
hydrochloride solution is made, previous to the actual 
determination, so as to allow for this error. A gram 
of the salt eliminates about 155 cc nitrogen, therefore, 
for the blank, 10 cc of‘the solution is accurately meas- 
ured out, mixed with the needful proportion of sodium 
acetate solution, diluted to 100 cc, and 50 cc trans- 
ferred to the dropping funnel; the end of this is drawn 
out at S and cut off at an angle so as to avoid the col- 
lection of bubbles of gas; before the funnel is fixed in 
place the stem is filled with water. When the greater 
portion of the air has been removed from the apparatus 
in the manner described above, the phenylhydrazine 
salt is allowed to mix with the Fehling’s solution, care 
being taken to prevent the water flowing from VW into 
A. When all has been added the funnel is washed 
out twice with hot water, which also is allowed to run 
into A. If the boiling is sufficiently brisk the evolu- 
tion of nitrogen is completed in 2-3 minutes. As 
soon as the bubbles are as small as those of the air at 
the commencement of the experiment the heating is 
stopped, the hot water in W replaced by cold, the ex- 
cess escaping into the dish C and the measuring tube 
removed to a cylinder of cold water. The actual de- 


~ 


_DETERMINATION OF CARBONYL. OHA 


termination is made immediately after the completion 
of the blank experiment and, if necessary, repeated a 
second or third time; since 200 cc Fehling’s solution 
readily liberates 150 cc nitrogen, the quantity taken in 
A amply suffices for three or four carbonyl determina- 
tions. 

As benzene is produced during the oxidation of the 
phenylhydrazine, a drop of it will be found floating 
on the surface of the water inside the measuring tube; 
this may be allowed for in measuring the gas or it may 
be removed. In the former case a little more benzene 
is introduced into the tube by means of a bent pipette, 
and, after remaining during a short time, the volume 
of nitrogen is read off in the ordinary manner; its 
reduction to 0° and 760 mm may be made by the 
help of the following table, the values in the second 
column being subtracted from the observed height of 
the barometer: 


Temperature. Tension of benzene + water. 
es Os 72-9. mm. 
16 76.8 
17 80.9 
18 85.2 
19 89.3 
20 93.7 
21 98.8 
2257" 103.9 
23 109. I 
24 114.3 
25 LEO.7 


The values given above are in part obtained by in- 
terpolation from Regnault’s results and are therefore 


78 RADICLES IN CARBON COMPOUNDS. 


subject to error; for this reason, and on account of the 
high vapor tension of benzene, its removal is advisable.* 
To accomplish this alcohol is added to 
the tube of nitrogen, which is placed in 
a cylinder of about its own length filled 
| with water (Fig. 12). A glass tube 5 
mm in diameter is bent into the form 
of a U as shown in the figure, the 
smaller limb terminating in a jet and 
being of such length that, when the 
Py bent portion rests on the bottom of the 
cylinder, the jet is several cm below 
the surface of the water. The longer 
limb rises about 40 cm above the sur- 
face of the water and is connected at 
ug the end by means of a piece of thick 
walled rubber tube with a dropping 
funnel. The U tube is completely 
filled with water and placed in the posi- 
tion shown in the figure. Alcohol 
\ (about 200 cc) is now allowed to flow 
from the funnel into the measuring tube ; 
} it issues from the jet in a fine stream 

Fic. 12. and absorbs the benzene vapor pres- 
ent in the nitrogen as well as that floating on the 
water; the alcohol is removed in a similar manner by 
washing with at least 400 cc of water, and the tube of 
nitrogen then removed to another cylinder of water, 
where, after a suitable interval, the volume of gas is 
read. The amount of carbonylic oxygen O is ob- 





























1 Benedikt and Strache, M. 14, 373. 


~ 


DETERMINATION OF CARBONYL. 79 


tained from the volume of nitrogen, corrected to 0° 
and 760 mm, by the expression: O = (g. V. — 2V,,.). 

0.07178 
15:9 100g = ORG. — 24) Os, 
where g is the weight of phenylhydrazine hydrochloride 
taken, V the volume of nitrogen evolved by I gram of 
this salt, S the weight of the compound employed, and 
V, the volume of nitrogen obtained at V.7.P. The 
theoretical value of V is 154.63 cc, but the value em- 
ployed in the calculation is that obtained in the blank 
experiment. 

If the phenylhydrazone is insoluble in water or dilute 
alcohol, or if sparingly soluble phenylhydrazides are 
formed, the preparation of the phenylhydrazone must 
be made in alcoholic solution; in this case the weight 
of the column of liquid in the funnel 7, Fig. 11, will 
not be sufficient to overcome the pressure of steam in 
the flask A. This difficulty may be surmounted by 
fitting the open end of the funnel with a rubber stop- 
per, carrying a tube and stop-cock. On blowing 
through the tube the alcoholic liquor is forced into the | 
flask, but great care is necessary, as the sudden evolu- 
tion of alcoholic vapor may eject liquid from flask A to 
B, or may even lead to an explosion. A second ob- 
jection to the use of alcohol is that, at its boiling- 
point, ketones do not always react quantitatively with 
phenylhydrazine. Both difficulties may be overcome 
by the use of recently boiled amylic alcohol as solvent; 
the portion of it which passes over with the nitrogen 
being subsequently removed, simultaneously with the 
benzene, by washing with alcohol and water. 








0.0012562. 


80 RADICLES IN CARBON COMPOUNDS. 


(2) PREPARATION OF OXIMES.' 


In the preparation of oximes the hydroxylamine is 
employed in the form of the free dase, the hydrochlo- 
ride, as potassium hydroxylaminesulphonate, or sinc 
dthydroxylamine hydrochloride. Aldoximes are ob- 
tained by treating aldehydes with an equimolecular 
proportion of hydroxylamine hydrochloride in concen- 
trated aqueous solution, adding sodium carbonate (0.5 
mol.), and allowing the mixture to remain at the 
ordinary temperature during 4-8 days. The oxime is 
extracted with ether, the solution dried over calcium 
chloride, and, after the removal of the ether, the resi- 
due rectified. An aqueous-alcoholic solution is used 
for aldehydes insoluble in water, and those that are 
readily oxidizable, such as benzaldehyde, are treated 
in flasks from which the air has been removed by 
means of carbonic anhydride.» Oximes of the car- 
bohydrates, which are so readily soluble in water that 
they cannot be separated from the inorganic salts re- 
sulting from the use of hydroxylamine hydrochloride 
and sodium carbonate or sodium hydroxide, are treated 
with the calculated quantity of free hydroxylamine in 
alcoholic solution; after several days the oxime gradu- 
ally crystallizes out. Alcoholic solution of hydroxyl- 
amine is prepared by intimately mixing the hydro- 
chloride with the necessary quantity of potassium 
hydroxide together with a little water, and then adding 
absolute alcohol; the clear liquid is afterwards sep- 





1°V. Meyer and Janny, B. 15, 1324, 1525. Janny, Jdid, 15, 2778; 
16, 170. 
2 Petraczek, /did. 15, 2783. 3 Wohl, /ézd. 24, 994. S., p. 367. 


~ 


‘DETERMINATION OF CARBONYL. 81 


arated from the precipitated potassium chloride.' The 
solution gradually acquires a slight yellow color,’ which 
may be obviated by substituting sodium ethoxide for 
the potassium hydroxide. 

Ketoximes are usually formed less readily than the 
aldoximes; for their preparation the ketone is mixed 
with the necessary proportions of sodium acetate and 
hydroxylamine hydrochloride in aqueous or alcoholic 
solution, and the liquid heated on the water-bath dur- 
ing I-2 hours, or the ketone, in alcoholic solution, 
may be heated in a sealed tube with the hydrochloride 
at 160°-180° during 8-10 hours,*? but sometimes, in 
these circumstances, instead of the oximes, derivatives 
of them are formed by intramolecular rearrangement.! 
In many cases it is highly advantageous to allow the 
carbonyl derivative and the hydroxylamine to react in 
strongly alkaline solution; the proportions which 
usually give the best results are ketone, in alcoholic 
solution (1 mol.), hydroxylamine hydrochloride (1.5—2 
mol.), alkaline hydroxide (4.5—6 mol.); the last two are 
dissolved in the smallest requisite quantity of water.> 
The reaction is often completed at the ordinary tem- 
perature in a few hours; occasionally heating on the 
water-bath is desirable. This method cannot of course 
be used with ketones or aldehydes that are attacked by 
alkali, nor in the preparation of dioximes which readily 
change into their anhydrides in the presence of alkali. 





1 Volhard, Ann, 253, 206, 2 Tiemann, B, 24, 994. 

3 Homolka, /ézd. 19, 1084. 

*K. Auwers and F, v. Meyenburg, /ézd. 24 (1891), 2386; A. W. 
Smith, /é¢d. 24, 4051; F. H. Thorp, Zézd. 26 (1893), 1261. 

5 Auwers, /éid. 22, 609. 


82 RADICLES IN CARBON COMPOUNDS. 


In such cases an acid liquid may be employed. Qui- 
none furnishes an example of this. In alkaline solu- 
tion it is reduced by hydroxylamine to hydroquinone, 
while in aqueous solution, in presence of hydrochloric 
acid and hydroxylamine hydrochloride, a dioxime is 
formed.! Some compounds, such as phenylglyoxalic 
acid, yield oximes both in alkaline and acid solutions.? 
Oximes of ketonic acids may be obtained by treating 
the alkali salt in neutral aqueous solution with hydroxy- 
lamine hydrochloride ; the precipitation of oxime usually 
commmences at once, especially if the liquid is 
warmed.® Sometimes it is advisable to convert the acid 
into its methyl ester and avoid the use of excess of hy- 
droxylamine hydrochloride so as to prevent the forma- 
tion of nitriles. Oily oximes may be converted into 
crystalline acetic acid derivatives R: N.O.CH,.COOH 
by heating with chloracetic acid (1 mol.), and potassium 
hydroxide (2 mol.), in alcoholic solution.5 

Potassium hydroxylamine sulphonate, supplied by 
the ‘‘ Badischen Anilin- und Sodafabrik,’’ under the 
name ‘‘ Reducirsalze,’’ has been employed, in aqueous- 
alcoholic solution, for the preparation of oximes;¢ in 
presence of free alkali it is hydrolysed, and the lib- 
erated hydroxylamine acts, in the nascent state, on the 
carbonyl compounds.’ It also possesses the advantage 
of cheapness. 





1 Nietzki and Kehrmann, B. 20, 614. a Si, By 37. 
3 Bamberger, /éid. 19, 1430. 
4 Garelli, Gazz. 21, 2, 2173. 
5 F, Tiemann, B, 31 (1898), $72, 
6 Kostanecki, /d:d. 22, 1344. 
7 Raschig, Ann, 241, 187. 


DETERMINATION OF CARBONYL. 83 


Zinc dihydroxylamine hydrochloride, ZnC\,.2NH,OH, 
has been used chiefly for the preparation of ketoximes! 
as its resolution into hydroxylamine and anhydrous zinc 
chloride facilitates the elimination of water. It is pre- 
pared? by adding zinc oxide (1 part) to hydroxylamine 
hydrochloride (2 parts) in boiling alcoholic solution. 
The boiling is continued in a reflux apparatus for a few 
moments, and the liquid allowed to cool. The com- 
pound is deposited as a crystalline powder which dis- 
solves sparingly in water or alcohol, but readily in solu- 
tions of hydroxylamine hydrochloride. 

Ortho- and paraquinones, and metadiketones do not 
react with hydroxylamine if several atoms of hydro- 
gen in the ortho-position are replaced by haloid atoms 
or alkyl groups. Aromatic ketones of the formula 


(CH,.C),C.COR, where R= phenyl or an _ alcohol 


radicle, are also.incapable of forming oximes;‘ indeed, 
the presence of carbonyl, which does not yield oximes, 
in such compounds as acids,® amides,® or esters’ may, 
by the production of hydroxamic acids, lead to errone- 
ous results. The statement that alkyl salicylates and 
hydroxylamine give salicylhydroxamic acid’ has been 
confirmed.* The unsaturated ketoalcohol camphor- 
oxalic acid. 


C:¢:OH.CO.OH 
CH =) 
CO 


1 Crismer, Bull. soc. chim. [3], 3, 114. #2843, R223. 

3 Kehrmann, /ézd. 21, 3315. Herzig and Zeisel, Zid. 21, 3494. Cf. 
Ibid 22, 1344. 

4'V. Meyer, /éid. 29, 836. Feit and Davies, /éid. 24,3546, Biginelli, 
Gazz. 24, 7, 437. Claus, J. pr. 45, 383. Baum, B. 28, 3209. 

5 Nef, Ann, 258, 282. 6 C, Hoffmann, B. 22, 2854. 

7 Jeanrenaud, /éid. 22, 1273. *A. Tingle, Am, Chem. Journ. 24, 52. 





? 


84 RADICLES IN CARBON COMPOUNDS. 


yields an additive compound 


CH.C.OH.CO.OH 
CAT td 
CO NH.OH . 
with hydroxylamine,’ and it has been subsequently 
shown that certain unsaturated ketones, such as pho- 
rone, behave in a similar manner.’ 


(3) PREPARATION OF SEMICARBAZONES.® 


The formation of well-crystallized derivatives of 
semicarbazine has proved extremely useful in the inves- 
tigation of terpene compounds which often yield liquid 
oximes, and phenylhydrazones that only crystallize with 
difficulty and readily undergo decomposition. As a 
rule the aldehyde or ketone combines with semi- 
carbazine- in equimolecular proportion, but ethylic 
aldehydophenylearbonate yields the compound 

C,H,0.CO.0.C,H,.CH:N.NH.CO.N:CH.C,H,.0.CO.OC,H;4 

Aliphatic ketones have varying velocities of interac- 
tion with different salts of semicarbazine, hence, by the 
successive addition of different semicarbazine salts to a 
mixture of such ketones,a separation of them may be 
effected (cf. p. 72).° 


Preparation of Semicarbazine Salts.® 


(A) Semicarbazine Hydrochloride. 
NH,.CO.NH.NH,. HCl 





1 Bishop Tingle, Am. Chem. Journ. 19, 408. 

2 C, Harries and F. Lehmann, B. 30, 231, 2726. 

8 Baeyer and Thiele, 7ézd, 27, 1918. 

4H. Cajar, /bid. 31 (1899). 2806. 

5 A, Michael, J. pr. 60 [2] (1899), 347. 

6 T. Curtius and K. Heidenrich, /éid. 52 [2] (1895), 465. 


DETERMINATION OF CARBONYL. 85 


is prepared from 


(2) Hydrazine sulphate,* 
(6) Nitrocarbamide.’ 


(2) Hydrazine sulphate (13 grams) is dissolved in 
water (100 cc), and neutralized with dry sodium car- 
bonate (5.5 grams); when cold, potassium cyanate (8.8 
grams) is added, and the solution allowed to remain 
overnight. A small quantity of hydrazodicarbonamide, 

NH,.CO.NH.NH.CO.NH,, is deposited which is some- 
_ what augmented on acidifying with dilute sulphuric 
acid. The amide is removed,and the acid liquid well 
shaken with benzaldehyde; the precipitate of benzal- 
semicarbazone which forms is separated, and well 
washed with ether. It is now carefully heated on the 
water-bath, in portions of 20 grams, with concentrated 
hydrochloric acid (40 grams), sufficient water being 
added to cause the hot liquid to become clear; the benz- 
aldehyde is removed by repeatedly extracting the hot 
liquid with benzene; when cold the aqueous solution 
deposits small needles of semicarbazine hydrochloride, 
which are removed, dried, and recrystallized from dilute 
alcohol. The purified compound forms prisms which 
decompose at 173°. The mother-liquors yield a further 
quantity of the benzal derivative when treated with 
benzaldehyde. In place of benzaldehyde acetone may 
be employed to separate the semicarbazine, the result- 
ing product requires 24 hours to separate, but is more 
easily decomposed than the benzal derivative. The 
mother-liquor may be treated with benzaldehyde or 





1 Thiele and O. Stange, B. 28, 32. 
? Thiele and Heuser, Ann, 288, 312, 


86 RADICLES IN CARBON COMPOUNDS. 


exactly neutralized, evaporated to dryness, and the 
residue extracted with acetone. The yield is 60 per 
cent.! 

(6) Commercial nitrocarbamide (225 grams) is mixed 
with concentrated hydrochloric acid (1700 cc), a little 
ice added, and the liquid made into a paste by the suc- 
cessive additions of small quantities of zinc-dust and 
ice; constant stirring is necessary, and the temperature 
must not exceed 0°. The operation may be carried 
out in an enamelled dish cooled by means of a freezing 
mixture; when it is completed the product is allowed 
to remain for a short time, the excess of zinc-dust re- 
moved, and the filtrate saturated with sodium chloride. 
Sodium acetate (200 grams) is now added, together 
with acetone (100 grams), and the liquid placed on ice 
or in a freezing mixture. In the course of several hours 
a double salt of zinc chloride and acetone semicarba- 
zone crystallizes out, it is collected and washed, first 
with sodium chloride solution and finally with a little 
water. The yield is 40-55 per cent. The zinc com- 
pound (200 grams) is digested with concentrated ammo- 
nium hydroxide (350 cc), and after some time the liquid 
is filtered; the residue consists of acetone semicarba- 
zone, which is converted into semicarbazine salts in 
the manner described above for the benzal derivative. 
Many ketones do not readily react with semicarbazine 
hydrochloride and the products obtained from some 
may contain chlorine; in such cases semicarbazine sul- 
phate should be employed. 





1 J. Thiele and O. Stange, Ann, 283 (1894), 19. 


DETERMINATION OF CARBONYL. 87 


(B) Preparation of Semticarbazine Sulphate. 


The filtrate from hydrazodicarbonamide, prepared in 
the manner described above, is cautiously made alka- 
line and shaken with acetone; the acetone semicarba- 
zone, which is deposited, is mixed with alcohol, and 
treated with the calculated quantity of sulphuric acid; 
the sulphate crystallizes out and is purified by washing 
with alcohol. 


Preparation of Semicarbazones.* 


Semicarbazine hydrochloride, dissolved in the mini- 
mum quantity of water, is mixed with the calculated 
amount of potassium acetate in alcoholic solution, and 
the ketone added, together with water and alcohol 
sufficient to give a clear homogeneous liquid. This is 
allowed to remain until the completion of the reaction, 
which is recognized by the deposition of crystals when 
the mixture is diluted with water, and, as in the case 
of hydroxylamine, may require from a few minutes to 
four or five days. Sometimes it happens that the de- 
posit produced is oily and only solidifies after several 
hours. The use of semicarbazine sulphate is illustrated 
by the preparation of ionone semicarbazone, which 
cannot be obtained from the hydrochloride. The sul- 
phate is used in a finely divided form and added to 
glacial acetic acid, in which the equivalent quantity of 
sodium acetate has been dissolved; after remaining at 
the ordinary temperature during twenty-four hours the 





1 Tiemann and Kriger, B. 28, 1754. 
2 Baeyer, /bid. 27, 1018 


88 RADICLES IN CARBON COMPOUNDS. 


solution of ionone is added, and the liquid allowed to 
remain three days longer. The product is poured into 
a considerable volume of water, extracted with ether, 
and the ether freed from acetic acid by treatment with 
sodium carbonate solution. After drying and removal 
of the ether, the residue is treated with ligroin to re- 
move some impurities, and the remaining product crys- 
tallized from a mixture of benzene and ligroin. In 
some cases the ketone is dissolved in glacial acetic 
acid,'! or free semicarbazine, prepared by treating a 
concentrated aqueous solution of the hydrochloride 
with absolute alcoholic sodium ethoxide solution, is 
employed.? 

The production of stereoisomeric semicarbazones of 
cyclic ketones has been investigated.° 

Should a ketone not yield a crystalline semicarbazone 
it is advisable to convert it into the aminoguinadine 
picrate, as these compounds are distinguished by the 
ease with which they crystallize. (Cf. p. 92). 


(4) PREPARATION OF THIOSEMICARBAZINE - 
DERIVATIVES. 


Thiosemicarbazine, NH,.CS.NH.NH,, is prepared 
by gently heating commercial hydrazine sulphate (50 
grams), water (200 cc) and calcined potassium carbonate 
(27 grams). When solution has taken place potassium 
thiocyanate (40 grams) is added, the liquid boiled for a 





1F, Tiemann, B. 28 (1895), 2192. 

2 R. Brener, dtd. 31 (1898), 2199. 

3. N, Zelinsky, /éid. 30 (1897), 1541. 

4M. Freund and A. Schander,. 67d. 29 (1896), 2501. 


DETERMINATION OF CARBONYL. 89 


few minutes, alcohol (200-300 cc) is added to precipi- 
tate potassium sulphate, and the filtrate evaporated 
until gas evolution begins. The product is treated 
with water, filtered, and the filtrate evaporated as be- 
fore. This treatment is repeated 4-5 times. . The 
yield of crude product is 70 per cent of the theoretical. 

Thiosemicarbazine readily reacts with aldehydes and 
ketones, the resulting thiosemicarbazones are separated 
from the excess of reagent by solution in alcohol or 
some other organic solvent, and then treated with an 
aqueous or alcoholic solution of silver nitrate. The 
salt formed is usually curdy; after washing and drying 
it is dissolved in water or alcohol, or suspended in 
ether according to the solubility of the thiosemicarba- 
zone, and the aldehyde regenerated by treatment with 
a mineral acid. In the case of compounds volatile with 
steam it is advantageous to use phthalic anhydride in- 
stead of the mineral acid.! 

The method is very generally applicable, and has 
been extremely useful in separating the aldehydes 
formed by the decomposition of gelatine. It cannot 
be employed for the purification of sugars on account 
of the solubility of the silver salts. Copper acetate, 
mercuric acetate, mercuric cyanide, and potassium 
mercuric iodide may be substituted for the silver 
nitrate; the resulting copper salts are usually amorph- 
ous, the others crystalline. 





1C, Neuberg and W. Neumann, B, 35 (1902), 2049. M. Freund 
and A, Schander, /éid. 2602. 


gO RADICLES IN CARBON COMPOUNDS. 


(5) PREPARATION OF SEMIOXAMAZINE 
NH,.CO.CO.NH.NH,,." 


Potassium hydroxide (9 grams) is dissolved in water 
(100 grams), and finely divided hydrazine sulphate (10 
grams) added; the liquid is diluted with its own vol- 
ume of alcohol, potassium sulphate removed, and the 
filtrate warmed on the water-bath with oxamethane 
until solution takes place. On cooling the semioxama- 
zine is deposited, and is purified by recrystallization 
from water. Semioxamazine readily yields crystalline 
derivatives with aldehydes, which, unlike many semi- 
carbazine derivatives, only occur in one form, but its 
interaction with ketones is irregular. 


(6) PREPARATION OF AMINOGUINADINE DERIVATIVES.? 


Preparation of Aminoguinadine Salts.’ 


Nitroguinadine (208 grams) is mixed with zinc-dust 
(700 grams),and sufficient ice and water to form a stiff _ 
paste; to this commercial glacial acetic acid (124 
grams), diluted with its own volume of water, is added, 
the mixture is well stirred, and great care taken to add 
ice so that during the 2-3 minutes required for the 
addition of the acid the temperature shall not exceed 
o°. The temperature is now allowed to rise gradually 
to 40°; at this stage the mixture is viscid and has a 
yellow color due to an intermediate product. The 
temperature is maintained at 40°—45° until a little of 
the filtered liquid ceases to yield a red color with 





1'W. Kerp and K. Unger, B. 30 (1897), 585. 
2 Baeyer, did. 27, 1919. 3 Thiele, Ann, 270, 23. 


DETERMINATION OF CARBONYL. 9! 


sodium hydroxide and a ferrous salt. The conclusion 
of the operation is usually indicated by evolution of 
gas and the formation of a frothy scum on the surface 
of the liquid. The product is filtered, the residue well 
washed with water, the washings and filtrate mixed 
with hydrochloric acid sufficient to liberate the acetic 
acid, and the whole concentrated to the smallest pos- 
sible bulk; it is then treated with alcohol, again evap- 
orated to expel water, and the solid boiled out with 
alcohol; this, when cold, -deposits aminoguinadine 
hydrochloride, which is further purified by recrystalli- 
zation from alcohol to which animal charcoal has been 
added. The pure salt melts at 163°. 


Preparation of Aminoguinadine Bicarbonate." 


The liquid obtained by the reduction of nitroguina- 
dine with zinc-dust and acetic acid is maintained 
slightly acid with acetic acid, evaporated to about 500 
cc, cooled, and treated with concentrated sodium or 
potassium bicarbonate solution to which a little am- 
monium chloride has been added to prevent the de- 
position of any zinc. The aminoguinadine salt is 
completely precipitated in twenty-four hours; it is 
sparingly soluble in hot water but suffers decomposi- 
tion, and when slowly heated it melts and decomposes 
a eae 

The nitrate,and the normal and hydrogen sulphates 
are prepared in a similar manner. 





1 Thiele, Ann, 302, 333. 


92 RADICLES IN CARBON COMPOUNDS. 


Preparation of Aminoguinadine Picrate Derivatives. 


Aminoguinadine hydrochloride is dissolved in a 
small quantity of water containing a trace of hydro- 
chloric acid,and the ketone added,together with suffi- 
cient alcohol to give a clear solution. The reaction is 
completed by boiling for a short time. The product is 
treated with water and sodium hydroxide solution in 
excess, and the liquid base extracted by means of 
ether. The ethereal solution is separated, the ether 
removed, the residual oil suspended in water, and 
treated with picric acid in aqueous solution, the picrate 
is quickly deposited in granular crystals which are puri- 
fied by recrystallization from concentrated or dilute 
alcohol. 

Some carbohydrate derivatives of aminoguinadine 
are known.! 


(7) PREPARATION OF PARAMINODIMETHYLANILINE 
- DERIVATIVES. - 


Condensation products of aldehydes and paraminodi- 
methylaniline may be prepared by mixing the con- 
stituents, with or without the addition of alcohol. The 
temperature of the liquid rises spontaneously, and the 
condensation product usually separates in crystals.? 





1 Wolff and Herzfeld, Z. Rib. 1895, 743. Wolff, B. 27, 971; 28, 
2613. 

2 A, Cahn, /did, 17, 2938. The literature of this subject is given in 
M. and J. Il, p. 515. 


DETERMINATION OF CARBONYL. 93 


(8) DERIVATIVES OF BARIUM SALTS OF AROMATIC 
AMINOCARBOXYLIC AND AMINOSULPHONIC ACIDS.! 


The substance (liquid), containing an aldehyde, is 
treated with a 10 per cent solution of the barium salt, 
the resulting insoluble compound is separated and steam 
distilled, so regenerating the aldelyde. The method 
has been applied to benzaldehyde, its homologues 
and derivatives, cinnamaldehyde, citral, citronellal, 
and salicylaldehyde. The barium salts of the follow-— 
ing acids have been employed: naphthionic, sulphan- 
ilic, m-aminobenzoic, 2-hydroxy-a-naphthylamine-3- 
carboxylic, and a-naphthylamine-5-sulphonic. 


'(9) OTHER DERIVATIVES OF ALDEHYDES AND 
KETONES. 


All primary acid hydrazides yield readily crystal- 
line compounds with aldehydes and ketones. itro- 
sobenzhydrazide is especially well adapted for the 
separation of small quantities of carbonyl compounds, 
from large bulks of solvent, in caseswhere phenylhydra- 
zine gives slimy precipitates. It is also useful for work 
with the sugars.’ 

Monopyrocatecholcarbonic hydrazide. 


CF OH-O:CO-NEENT: 
quickly condenses with aldehydes but not with ketones; 


the resulting compounds crystallize easily, are soluble 
in alkalis, and are reprecipitated by acids. 





1 Journ, Chem, Soc. 82 (1902), i. 376. German Patent, 124, 229. 
2 T. Curtius, J. pr. 50 [2] (1894), 283; B. 28 (1895), 523. 
3 A. Einhorn, Ann, 300 (1898), 136. 


94 RADICLES IN CARBON COMPOUNDS. 


DETERMINATION OF METHYLENE>CH,.! 


A quantity of substance sufficient to yield 0.20-0.25 
gram phloroglucide is heated during 2 hours at 70°—80° 
with water (5 cc), hydrochloric acid sp. gr. 1.19 
(15 cc), and slight excess of pure phloroglucinol in 
aqueous solution (15 cc). The precipitate is collected 
on a Gooch porcelain filter, and the filtrate again 
heated with more concentrated acid; if a further pre- 
cipitate forms another experiment must be made using 
water (5 cc), concentrated sulphuric acid (10 or 20 cc), 
and phloroglucinol solution (10 cc). After filtration, 
the phloroglucide C,H,O, is dried at 95°—98° during 4 
hours, and weighed, with due precautions against the 
absorption of moisture. One part of formaldehyde and 
I part of methylene =—4.6 and 9.857 parts of phlo- 
roglucide respectively. The method is sufficiently ac- _ 
curate to distinguish easily the presence of I, 2, or 3 
CH, groups in the molecule; it has been chiefly tested 
with formaldehyde and its condensation derivatives 
with sugars, but appears to be generally applicable. 





1G, H. A. Clowes, B. 32 (1899), 2842. 


CHAPTER IV. 


DETERMINATION OF THE AMINO NH,; NITRILE, CN; 
I ir It 
AMIDE CO.NH,; IMIDE NH; METHYL IMIDE N.CH,; 


AND ETHYL IMIDE N.C,H, GROUPS. 


DETERMINATION OF THE AMINO GROUP 
(NETS): 


Different methods are employed for the determina- 
tion of the amino group according to whether the com- 
pound is an aromatic or aliphatic amine. 


(A) Determination of Aliphatic Amino Groups. 


These are determined: 

(1) By means of nitrous acid. 

(2) By analysts of the salts and double salts. 

(3) By acetylation. 

(4) TYitration with enanthaldehyde. 

(1) Netrous Acid Method.—A\phatic amines react 
with nitrous acid in accordance with the equation 


RNH, + HNO,>ROH + N, + H,O. 


The first method suggested for the determination of the 

nitrogen consisted in liberating it in an atmosphere of 

nitric oxide, which was then absorbed by means of fer- 
95 


96 RADICLES IN CARBON COMPOUNDS. 


rous sulphate solution.’ The following process is much 
more convenient. The substance, dissolved in just 
sufficient dilute sulphuric acid to give a neutral solu- 
tion, is placed in a flask provided with a trebly bored 
stopper. If possible a distillation bulb should be em- 
ployed having a capillary tube fused to it. A dropping 
funnel is fitted to the stopper of the flask, the leg being 
drawn out, bent upwards, and passed below the surface 
of the liquid; itis filled with distilled water at the com- 
mencement of the experiment. The third tube of the 
flask, or the side tube of the distillation bulb, is fitted 
by means of an air-tight stopper almost to the bottom 
of a second distillation bulb. This has its side tube 
suitably bent, and connected with a Leibig’s potash 
bulb filled with potassium permanganate solution (3 
per cent),containing sodium hydroxide (about I gram). 
The gas delivery-tube is attached to the potash bulb, | 
and dips below the mouth of the measuring vessel, 
which is half filled with mercury and half with potas- 
sium hydroxide (sp. gr. = 1.4). The air is displaced 
from the apparatus by a slow current of carbonic 
anhydride, which may be obtained pure and free from 
air by dropping dilute sulphuric acid (50 per cent, sp. 
gr. = 1.4) into a concentrated solution of potassium 
carbonate (sp. gr. = 1.45-1.5).2, When the air is 
expelled, the measuring tube is placed in position,and 
a slight excess of potassium nitrite solution added by 
means of the dropping-funnel. The reaction is com- 





1 R. Sachsse.and W. Kormann, Landwirthsch. Vers,-Stationen, 27, 
321. Z. anal. Ch. 14, 380. 
2 Fr. Blau, M. 13, 280. 


DETERMINATION OF THE AMINO GROUP, ETC. 97 


pleted by heating on the water-bath and the addition 
of a little dilute sulphuric acid. 

(2) Analysts of Salts and Double Salts.—The prepa- 
ration of most of these is too well known to require 
comment. Of the simple salts the hydrochlorides 
sometimes can only be induced to crystallize in a state 
of purity by the action of anhydrous hydrogen chloride 
on a solution of the base in ether, free from alcohol 
and moisture. The chromate and picrate,' especially 
the latter, usually crystallize readily. The mercurt- 
chloride, RHgCl’, has occasionally been of service in 
cases where the chloraurate or chloroplatinate are oily 
or unstable (cf. p. 105). 

(3) Acetylation.—This is described in connection 
with the aromatic amines, p. 106. 

(4) Tetration with enanthaldehyde. The base (2-4 
grams) is dissolved in benzene (2-3 vols.), a few pea- 
sized fragments of fused calcium chloride added, and 
the aldehyde pure, or in benzene solution, gradually 
run in from a burette. The operation is completed so 
soon as further addition of the aldehyde fails to produce 
aturbidity. 139 grams aldehyde = 2 grams hydrogen 
in the amine.’ 


(B) Determination of Aromatic Amino Groups. 


The following methods are employed for the deter- 
mination of primary aromatic amines: 
(1) Z2tration of the salts. 
(2) Preparation of dtazo derivatives. 
(a) By conversion into an azo dye. 





1 Delépine, Bull. 15, 53. 2H. Schiff, Ann. 159 (1871), 158. 


98 RADICLES IN CARBON COMPOUNDS. 


(6) Lndirect method. 
(c) Azotmide method. 
(2) Ly means of the Sandmeyer-Gattermann re- 
action. 
(3) Analysts of salts and double salts. 
(4) Acetylation. 


(1) TITRATION OF THE SALTS.! 


(1) Salts of aromatic amines, in aqueous or alcoholic 
solution, give an acid reaction with rosolic acid or 
phenolphthalein. The salt, preferably the hydrochlo- 
ride or sulphate, is dissolved in water or dilute alcohol, 
phenolphthalein added, and the titration carried out in 
the ordinary manner with potassium hydroxide. _ 

(II) Many free bases may be directly titrated with 
hydrochloric acid, methyl orange being used as an 
indicator. ? 

(III) A large number of alkaloids may be determined? 
by dissolving about 0.2. gram in a known volume of 
N /20 hydrochloric acid (30 cc),adding, in excess, neu- 
tral iodopotassium iodide solution (Wagner’s reagent), 
containing iodine (10 grams), and potassium iodide (15 
grams) in I liter. The mixture is vigorously shaken 
until no further precipitate is formed and the super- 
natant liquid is dark red and perfectly clear; it is then 
diluted to1oocc. After filtering, 50 cc are decolorised 
by means of a few drops of sodium thiosul phate solution 
(10 per cent), and titrated with V/20 potassium hydrox- 
ide, in presence of phenolphthalein. Should the alkaloid 





1 Menschutkin, B. 16, 316. 
2H. M. Gordin, dd. 32 (1899), 2871. 


of 


DETERMINATION OF THE AMINO GROUP, ETC. 99 


yield a less soluble compound with potassium mercuric 
iodide (Mayer’s reagent) than with Wagner’s reagent, 
the former is substituted for the latter. The V/20 acid 
is best standardized in the above manner by means of 
some pure alkaloid such as morphine. The following 
factors may be of service: I cc acid will be equivalent 
to 0.0184 gram hydrastine, 0.0160 gram strychnine, 
0.0102 gram caffeine (cryst.), 0.0139 gram atropine, 
and 0.0146 gram cocaine, if it is found, by experiment, 
that I cc acid = 0.0137 gram morphine (anhydrous). 
In the titration of caffeine 50 instead of 30 cc acid 
should be employed. Berberine and colchicine can 
not be determined by this method. 


(2) PREPARATION OF DIAZO-DERIVATIVES. 


(a) Conversion of the Base into an Azo Dye.' 

The base, for example aniline (0.7—0.8 gram), is 
dissolved in hydrochloric acid (3 cc), and diluted with 
water and ice to 100 cc. A titrated solution of 
‘¢R-salt,’’ sodium 2:3:6 naphtholdisulphonate, is pre- 
pared, of such strength that a liter is equivalent to 
about 10 grams of naphthol. The solution of the 
hydrochloride is cooled to 0°, sodium nitrite added in 
quantity equivalent to the aniline or other base present, 
and the mixture gradually poured into a measured 
quantity of the sulphonate solution, which has been 
treated with sodium carbonate in excess. The dye pro- 
duced is precipitated by means of sodium chloride, fil- 
tered,and the filtrate tested with benzenediazonium chlo- 
ride solution, and with R-salt to determine whether the 





1 Reverdin and De la Harpe, Ch. Ztg. 13, I. 387, 407; B. 22, 1004. 


100 RADICLES IN CARBON COMPOUNDS. 


latter or the base is in excess. By repéating the ex- 
periment it is possible to find the volume of R-salt solu- 
tion necessary to combine with the diazo-derivative of 
the base originally taken. 

The following method has been applied to aniline, 
ortho- and paratoluidine, metaxylidine, and sulphanilic 
acid.t. A known quantity of the base is diazotized and 
made up toa certain volume; it is then immediately 
added from a burette to a solution of ‘‘ Schifer’s salt,’’ 
sodium 2:6-naphthol sulphonate, of known strength, 
which has been mixed with sodium chloride and a few 
drops of ammonium hydroxide, the addition being con- 
tinued so long as a precipitate forms. The end point 
is determined by bringing a drop of the clear superna- 
tant liquor into contact with a drop of the diazo-solution 
on filter paper. The progress of the reaction can be 
followed by the. intensity of the red color produced at 
the point of contact of the two liquids on the paper. 
Towards the end of the operation the color is only 
visible in the middle of the moist circle. In the case 
of a readily soluble dye, such as that given by sulpha- 
nilic acid, the paper must be covered with a thin crust 
of sodium chloride and the test portions allowed to fall 
on to it; more sodium chloride must also be added to 
the naphtholsulphonate solution. 

The method can be applied* as a colourimetric one to 
the determination of very small quantities of methylic 
anthranilate in ethereal oils, or, where larger quantities 
_ of this compound are being dealt with, an alkaline 

solution of @-naphthol may be substituted for the disul- 





1R. Hirsch, B. 24, 324. 2 E. Erdmann, /d7d. 35 (1902), 24. 


DETERMINATION OF THE AMINO GROUP, ETC. IOI 


phonate. The resulting dye is insoluble in water. 
The end point is determined as in the case of the 
‘«R-salt.’’ The method is stated! not to be quantita- 
tive when the ester is mixed with large quantities of 
terpenes, but it sharply distinguishes between methylic 
anthranilate and methylic methylanthranilate. When 
these occur together a combination of the two methods 
is advantageous, one-half the precipitate (see below) 
being diazotised, and the other titrated and hydrolysed. 
The difference between the results gives the amount of 
methylic methyl anthranilate present. Where the 
latter is absent the determination may be made more 
simply by dissolving the oil? in dry ether (2-3 parts), 
cooling to 0° or lower, and gradually adding a well- 
cooled mixture of concentrated sulphuric acid and ether 
(1:5 vols.). The resulting precipitate is collected 
on a filter, washed well with dry ether, dissolved in 
water, and titrated with N/2 potassium hydroxide and 
phenolphthalein. After the titration, excess of the 
potash is added, the liquid heated for half an hour on the 
water-bath, and the product titrated with N/2 sulphuric 
acid. The percentage of ester (#) in the oil is calcu- 


i cn O75 G 
s 


lated by the formula + = 100 where a 





= cc potash required for the hydrolysis, and s the 
weight of substance taken. The first titration serves 
as a check. 


(6) Indirect Method. 


This is extensively employed fortechnical purposes, - 
and consists of an inversion of a method for the deter- _ 





1G. Hesse and O. Zeitschel, B. 35 (1902), 2355. 
2 Ibid, 34 (1901), 2966. 


102 | RADICLES IN CARBON COMPOUNDS. 


mination of nitrous acid.1 The base is treated with 
three times its weight of hydrochloric acid, and the 
mixture dissolved in so much water that the solution 
contains 0.01 to 0.1 gram equivalent of the base. The 
solution is maintained at O° by means of ice, and 
titrated with sodium nitrite solution, potassium iodo- 
starch paper being used as indicator; the operation is 
ended when a drop of the mixed liquids gives a blue 
coloration with the paper. The nitrite solution should 
be about WV/1o. It is prepared* by dissolving the 
nitrite in 300 parts of cold water, and its titre is ob- 
tained by adding /V/IO potassium permanganate solu- 
tion until a distinct permanent red coloration is 
obtained; two or three drops of dilute sulphuric acid 
are now added, then, immediately, excess of the per- 
manganate, the liquid is made strongly acid with sul- 
phuric acid, heated to boiling, and the excess of 
permanganate determined by means of JV/IO oxalic 
acid solution. 


(c) Azotmide Method.* 


This is specially applicable to compounds containing 
amino groups linked to different nuclei. The azoimides 
are prepared by the action of ammonia on the diazoper- 
bromides’ and, on account of the large content of nitro- 
gen in the former, their analysis is peculiarly well 
adapted for the determination of the number of diazo- 





1 A. G. Green and S. Rideal, Ch. N. 49, 173. 

?L. P. Kinnicutt and J. U. Nef, Am. Chem. Journ. 5, 388. Fre- 
senius’ Zschr. 25, 223. 

$ Meldola and Hawkins, Ch. N, 66, 33. 

4 Griess, Ann. 137, 65. 


DETERMINATION OF THE AMINO GROUP, ETC. 103 


tisable groups in the molecule. Details of the method 
of preparing azomides have been given by various 
chemists. 


(2) Sandmeyer*-Gattermann's* Reaction. 


The determination of the amino group is often con- 
veniently accomplished by converting it into the diazo- 
derivative and replacing the nitrogen by chlorine; as 
a rule the diazo-compound is not isolated. The fol- 
lowing example‘ will serve’ to illustrate the method: 
Metanitraniline (4 grams) and concentrated hydro- 
chloric acid, sp. gr. = 1.17 (7 grams), are dissolved 
in water (100 grams), and IO per cent cuprous chloride 
solution (20 grams) added; the mixture is heated 
almost to boiling in a reflux apparatus, and sodium 
nitrite (2.5 grams), dissolved in water (20 grams), is 
gradually run in by means of a dropping funnel, the 
mixture being well shaken during the addition. Nitro- 
gen is evolved, and a heavy brown oil collects which 
solidifies when cooled with ice, and is purified by dis- 
tillation. As a rule these chloro-derivatives are vola- 
tile with steam; if not they are purified by means of 
ether or benzene. 

The above method is the one originally proposed by 
Sandmeyer; by means of it chloro-compounds may 
be readily obtained from diamines which cannot be 
diazotised in the ordinary manner. The cuprous chlo- 
ride employed is prepared by boiling crystallized cop- 
per sulphate (25 parts) and anhydrous sodium chloride 





1 Nélting, Grandmougin, and O. Michel, B. 25, 3328. Curtius and 
Dedichen, J. pr. [2], 50, 250. 
2B. 59,3033. 3 Ibid. 23, 1218. * Jbid. 17, 2650. 


104 RADICLES IN CARBON COMPOUNDS. 


(12 parts) with water (50 parts); some sodium sulphate 
crystallizes out, and when the reaction is completed 
the product is mixed with concentrated hydrochloric 
acid (100 parts), and copper turnings (13 parts), the 
mouth of the flask is loosely closed, and the mixture 
boiled until the liquid becomes colorless. Sufficient 
concentrated hydrochloric acid is now added to bring 
the weight of the mixture to 203.6 parts, since only 
6.4 parts of the copper actually dissolve, 197 parts of 
solution are obtained which contains 0.2 gram mole- 
cules of CuCl. The filtered solution may be retained 
a considerable time in a well-closed bottle containing 
carbonic anhydride.’ 

Cupric chloride is reduced to cuprous chloride by 
hypophosphorus acid,” hence, in place of the cuprous 
chloride solution prepared according to the foregoing 
method, a mixture of hydrochloric acid, copper sul- 
phate solution, and sodium hypophosphite may be 
employed.* 

The use of finely divided copper instead of cuprous 
chloride has been suggested ;* amongst other advantages 
the reaction proceeds at the ordinary temperature, and 
the yield is frequently improved. The copper is pre- 
pared by adding zinc-dust, through a fine sieve, toa 
cold saturated solution of copper sulphate until only a 
faint blue color remains, the product is well washed by 
decantation with large quantities of water, the remain- 
ing zinc removed by digestion with highly dilute hydro- 
chloric acid, and the copper filtered and washed with 
water until neutral; it is preserved in the form of a paste 





1 Feitler, J. pr. 4, 68. : 2A. Cavazzi, Gazz. 16, 167. 
3 A. Angeli, /d¢d. 21, 2, 258. * Gattermann, B. 23, 1218. 


DETERMINATION OF THE AMINO GROUP, ETC. 105 


in well-closed bottles. The following example will 
illustrate the method of working: Aniline (3.1 grams) 
is mixed with 40 per cent hydrochloric acid (30 
grams), and water (15 cc), the liquid is cooled to 0° 


_ and a saturated aqueous solution of sodium nitrite (2.3 


grams) quickly added, the liquid being vigorously 
stirred, preferably by means of a turbine; the reaction 
is completed in one minute. Finely divided copper (4 
grams) is now gradually added to the diazo solution, 
which is well stirred; the reaction requires 15—30 min- 
utes for completion, this is signalized by the particles 
of copper ceasing to be carried to the surface of the 
liquid by the escaping bubbles of nitrogen. The chlo- 
robenzene is removed by steam distillation. 


(3) ANALYSIS OF SALTS AND DOUBLE SALTS. 


The remarks on the salts of aliphatic amines (p. 97) 
apply generally to those of the aromatic series; the 
accumulation of negative groups in their molecules often 
completely prevents the formation of salts. Asa rule 
the chloraurate contains one atom of gold for each 
amino group, and the chloroplatinate one atom of plati- 
num to two amino groups, but amino pyridine platino- 
chloride has the formula (C,H,N,),.H,PtCl,.' Sometimes 
the alkyl haloid salts are of service, but many primary 
bases do not form them.” In presence of secondary or 
tertiary amino groups the method yields fallacious re- 
sults. The production of salts is not confined to nitro- 
gen derivatives, many oxygen compounds (oxonium 
bases) yield them, dimethylpyrone gives, amongst 





aM. 26,176. ? Hofmann, Jahresbericht (1863), p. 421. 


106 RADICLES IN CARBON COMPOUNDS. 


others, a chloroplatinate (C,H,O,),H,PtCl,' and certain 
phenol derivatives yield hydrochlorides and picrates.? 
‘¢Sulphonium ’’? and ‘‘carbonium’’* bases have also 
been described. 

Abnormal chloraurates of isopropylamine, piperi- 
dine, 1-methylpiperidine, 2~—5-dimethylpyrrolidine and 
quinoline have also been described,® they have the 
formula (NR,),AuCl,, and are readily resolved into the 3 
normal derivatives NR,AuCl, + NR,CI. 


(4) ACETYLATION. 


The methods of acetylation described for the deter- 
mination of hydroxyl are also applicable to the amino 
group (cf. pp. 6, 97, 112). . 

A number of amines, notably a-naphthylamine, may 
be acetylated in aqueous solution. The following 
method gives excellent results with aniline; some modi- 
fications would probably have to be introduced for other 
compounds. The amine solution, freed from tin, is 
highly concentrated, neutralized with soda, and satu- 
rated sodium acetate solution added in quantity equiva- 
lent to 85 per cent of the hydrochloride present; 10 
cc of this solution are titrated with N/Io potassium 
hydroxide, with litmus as indicator. To the remainder 
of the solution a sealed bulb containing a weighed quan- 





1 Collie and Tickle, Journ, Chem. Soc. 75, 712. 

2C. Bilow & H. Grotowsky, B. 35 (1902), 1800. Cf. A. Baeyer & 
V. Villiger, 7ézd. 34 (1901), 2679 et seq. 

3 F, Kehrmann, /éid. 32 (1899), 2602. 

4P. Walden, /ézd. 35 (1902), 2018, 

5G, Fenner and J, Tafel, /dzd. 32 (1899), 3220. 

6 J. Pinnow, /éid, 33 (1900), 418. 


DETERMINATION OF THE AMINO GROUP, ETC. 107 


tity of acetic anhydride is added, the bulb broken, and 
the contents rapidly mixed. A second titration of 10 
cc of this liquid is then made, any solid acetyl deriva- 
tive being removed by means of a dry filter. 

Thiacetic acid readily yields acetyl derivatives with 
aromatic amines on simple mixing.!_ Benzylidenaniline 
yields an unstable additive product, and trichlorethy- 
lidinediphenamine has one C,H,NH group acetylated, 
and the other replaced by SH on treatment with 
thiacetic acid.” 

The action of benzene sulphonic chloride, p-toluene- 
sulphonic chloride, p-bromobenzenesulphonic chloride, or 
m-nitrobenzenesulphonic chloride often affords a means 
of separating primary, secondary, and tertiary amines, 
as the first two interact, and the third does not. The 
reaction is carried out as in the case of hydroxy] deriv- 
atives (cf. p. 6). The products of primary and secon- 
dary amines frequently differ considerably in solubility.° 

Amino acids such as alanine, leucine, and tyrosine 
readily yield benzoyl derivatives by treatment with ben- 
zoyl chloride and sodium bicarbonate. * 

The separation of such compounds is often more 
readily accomplished by use of benzene sulphonic chlo- 
ride (1.5 mol.), and potassium hydroxide solution (22 
per cent).° A better reagent for hydroxyamino acids 
and complicated derivatives of the glycylglycine series 
is f-naphthalenesulphonic chloride; it is readily pre- 





1B. Pawlewski, B. 31 (1898), 661. dz, 35 (1902), IIO. 

2 A. Eibner, /ézd. 34 (1901), 657. 

3 W. Solonnia, J. Russ, Chem. Soc. 31 (1899), 640. Journ. Chem. Soc. 
78 (1900), i. 147. W. Marckwald, B. 32 (1899), 3512. 

4 E. Fischer, /ézd. 32, 2454. 

5 E. Fischer, /étd. 33 (1900), 2380; 34 (1901), 448. 


108 RADICLES IN CARBON COMPOUNDS. 


pared ', and most conveniently purified by distillation 
under a pressure of 0.3 mm and subsequent crystalliza- 
tion from benzene. The amino acid is dissolved in N 
sodium hydroxide solution (1 mol.) and mixed with the 
chloride (2 mol.) in ethereal solution; the mixture is 
shaken by a machine at the ordinary temperature, and 
at intervals of I-1.5 hours three times the above quan- 
tity of N alkali is added. At the conclusion of the 
experiment the aqueous liquid is separated, filtered, 
treated, if needful, with animal charcoal,and the naph- 
thalenesulphonic derivative precipitated by hydrochloric 
acid in excess.’ 


(5) ALKYLATION. 


Amino groups in certain leuco-bases and coloring 
matters are easily methylated ° by heating a solution of 
the substance with zinc-dust, hydrochloric acid, and 
formaldehyde at 75°—80°; the decolorised liquid is sub- 
sequently oxidised, either by exposure to air, or by lead 
peroxide and acetic acid. © 

The remarks on dimethylsulphate (p. 32) apply also 
to the alkylation of amino- or imino-compounds. It is 
usually employed in ethereal solution without alkali.4 


DETERMINATION OF THE NITRILE GROUP 
| (C:N.) 
The nitrile radicle is determined by hydrolysis, the 
resulting ammonia or acid being collected. 


(a) Prolonged boiling with hydrochloric acid is 
usually sufficient to cause hydrolysis; the product is 





1J. pr. 47 [2], 94. ? E. Fischer, B. 35 (1902), 3779. 
3M. Prud’homme, Bull. 23 (1900), iii. 69. 
4 F, Ullmann and P, Wenner, B. 33 (1900), 2476, 


DETERMINATION OF THE AMINO GROUP, ETC. 109 


then treated with alkali in excess, and the ammonia 
distilled off and determined in the ordinary manner. 

(6) A-Hydroxycyancamphor is unstable towards 
alkalis, and resists hot hydrochloric acid, and sul- 
phuric acid (60 per cent), but is readily hydrolysed 
by solution in fuming sulphuric acid at the ordinary 
temperature, and subsequent dilution. The resulting 
mixture of amides was converted into acids by pro- 
longed heating with fuming hydrobromic acid.! 

(c) Should the hydrolysis only take place in the pres- 
ence of aqueous or alcoholic alkali an apparatus similar 
to that employed in Zeisel’s method for the determina- 
tion of methoxyl is used (Figs. 2, 3, 5, pp. 39, 40, 42). 
A current of air, freed from carbonic anhydride, is 
passed through the apparatus, and the bulbs are filled 
with concentrated alkali solution; the ammonia is most 
readily determined as the chloroplatinate. At the 
conclusion of the experiment the flask A will contain 
the alkali salt of the acid produced, and may be treated 
by one of the methods described for the determination 
of carboxyl (Chapter IT). 

(2) The hydrolysis of nitriles ? may be hindered by 
stereo-chemical influences, especially in the case of 
diortho-substituted compounds,* just as the correspond- 
ing acids esterify with difficulty, or not at all, under 
the influence of hydrogen chloride. The nitriles in 
question, although they resist prolonged heating at a 





1 A. Lapworth and E, M. Chapman, Journ. Chem. Soc. 79 (1901), 378. 

2M. and J. Il, p. 545. 

3 A. W. v. Hofmann, B. 17, 1914; 18, 1825; Stallburg, Ann. 278, 
209. Cain, B. 28, 969. V. Meyer and Erb, /éid. 29, 834, foot-note. 
Sudborough, Journ. Chem. Soc. 67, 601. 






{BRAS 
VV SEnce i aes 


UNIVERSITY 
OF 
CALIFORNIK- 


IIo RADICLES IN CARBON COMPOUNDS. 


high temperature in a sealed tube with hydrochloric 
acid, are all converted into amides by continued boil- 
ing with alcoholic potassium hydroxide.! The amide 
is hydrolysed to the acid in the manner described in 
the following section. Cyanmesitylene? requires boiling 
during seventy-two hours with alcoholic potassium hy- 
droxide, and triphenylacetonitrile * needs fifty hours 
boiling with the same reagent to produce the amide. 
Some nitriles that are otherwise resistant may be hy- © 
drolysed by heating at 120°-130° during an hour with 
go per cent sulphuric acid (20-30 parts). The resulting 
amide is converted into the acid by means of -nitrous 
acid‘ (cf. following section). Unhydrolysable nitriles 
have also been described.°® 

(e) Certain amides may be obtained by the action of 
alkaline hydrogen peroxide at 40° on the nitriles; the 
resulting compounds are then treated in the manner 
described on p. III. 

(7) Some nitriles may be reduced to the correspond- 
ing amine by means of zinc and hydrochloric acid? or 
sodium and alcohol.§ 


DETERMINATION OF THE AMIDO GROUP 
(CO.NH,). 

The amido group is determined by hydrolysis, in a 

similar manner to the nitrile group (preceding section). 





1 Bouveault, S. p. 80. Hantzsch and Lucas, B. 28, 748. 

2,V. Meyer and Erb, Jézd. 29, 834. 3 V. Meyer, /did. 28, 2782, 

* Sudborough, Jour. Chem. Soc. 67, 601. Minch. B. 29, 64. 

5 J. Deinert, J. pr. 52, [2] (1895), 431. Radziszewsky, B. 7, 18, 355. 
J. K, Auwers and A, J. Walker, /ézd. 31 (1899), 3044. 

6 Claus and Wallbaum, J. pr. 56, 52. 

? Mendius, Ann. 121 (1862), 129. ® Ladenburg, B. 18 (1885), 2956. 


DETERMINATION OF THE AMINO GROUP, ETC. III 


The method employed for the hydrolysis of very stable 
amides ' is best illustrated by its application to the prep- 
aration of triphenylacetic acid.2 The finely divided 
amide (0.2 gram) is gently warmed with concentrated 
sulphuric acid (1 gram) and the clear solution cooled in 
ice, sodium nitrite (0.2 gram), dissolved in water (I 
gram), cooled to 0°, is added very slowly by means of a 
capillary tube; when the addition is complete the test- 
tube containing the mixture is placed in a beaker of 
water and gradually heated. ' The evolution of nitro- 
gen commences at 60°-70°, and is completed at 
80°-90°; finally the tube is heated in boiling water for 
3-4 minutes, but not longer. When cool, ice is added 
to the liquid, the precipitated solid collected, and puri- 
fied by solution in dilute sodium hydroxide and precipi- 
tation with sulphuric acid. It is highly desirable to 
use the exact theoretical quantity of sodium nitrite dis- 
solved in the smallest possible volume of water. The 
amide may also be dissolved in sulphuric acid (20-30 
per cent), and to the boiling liquid sodium nitrite solu- 
tion (5-10 per cent) added; (1.5-2 mol. for each 
CO.NH, group). The boiling is continued until gas 
evolution ceases.‘ 

y-Hydroxyvaleric amide is completely hydrolysed 
only if it is boiled down to dryness with dilute hydro- 
chloric acid, or heated in a reflux apparatus for 2 hour ina 
current of air.° Stereo-chemical influences are effective in 





1 Bouveault, Bull. [3], 9, 370. 7G. Heyl and V. Meyer, B. 28, 2783. 
3 Sudborough, Jour, Chem. Soc. 67, 604. 

4L. Gattermann, B. 32 (1899), 1118. 

5 E. L. Neugebauer, Ann. 227 (1885), 105. 


112 RADICLES IN CARBON COMPOUNDS. 


hindering the hydrolysis of amides, as they are in that 
of the nitriles. 


DETERMINATION OF THE IMIDE GROUP 
| (NH). 


The following methods are employed for the deter- 
mination of the imide group: 

(1) Acetylation. 

(2) Alkylation. 

(3) Analysis of salts. 

(4) Elimination of the imidogen as ammonia. 


(1)ACETYLATION OF IMIDES (SECONDARY AMINES). 


Imides may be acetylated by any of the methods 
employed for the determination of hydroxyl which are 
described in Chapter I. The reaction usually takes | 
place without difficulty, and therefore an indirect 
method ? may be utilized. A weighed quantity of the 
compound (about I gram) is placed in a flask, fitted to a 
reflux apparatus, and acetic anhydride (about 2 grams) 
quickly added. The anhydride should be added from 
a suitably stoppered vessel, which is weighed before 
and after the addition. The mixture is allowed to re- 
main at the ordinary temperature during about thirty 
minutes, water (50 cc) is then added, and the liquid 
heated on the water-bath during forty-five minutes; the 
solution is now cooled, diluted to a definite volume, 
and titrated with sodium hydroxide of known strength, 
phenolphthalein being used as indicator. 





1 A bibliography of the subject is given in M. and J, II, p. 545. 
2 Reverdin and De la Harpe, B. 22, 1005. 


DETERMINATION OF THE AMINO GROUP, ETC. I13 


The process was specially worked out for methylani- 
line, hence, for other imides, the duration of the heat- 
ing and the temperature require modification according 
to the readiness with which they react. It may be 
desirable to heat in a sealed tube, or in a dry closed 
flask, the mixture being constantly shaken, and the 
anhydride diluted with ten volumes of dimethylaniline.! 


(2) ALKYLATION: OF IMIDES. 


Some imide groups may be methylated by dissolving 
the compound in alkali and gradually adding methylic 
iodide; the mixture is constantly shaken and main- 
tained at the ordinary temperature. The method has 
been extensively employed in the investigation of purin 
and uric acid derivatives? (cf. p. 108). 


(3) ANALYSIS OF SALTS. 


The remarks on the analysis of salts of primary 
amines (pp. 97, 105) apply equally to those of secon- 
dary ones. 


(4) ELIMINATION OF IMIDOGEN AS AMMONIA. 


The hydrolysis of the acid imides is usually carried out 
by prolonged boiling with hydrochloric acid either in an 
open vessel or under pressure in a sealed tube. The 
liquid is then made alkaline, the ammonia or amine 
volatilized into hydrochloric acid, and the excess of 





1H. Giraud, Bull. (3), II. 142. 
* E. Fischer, B, 28, 2479; 30, 569, 3094 ; 32, 453. C. (1897), II, 157. 


Il4 RADICLES IN CARBON COMPOUNDS. 


the latter determined by titration or, in some cases, by 
means of the chloroplatinate. 


DETERMINATION OF METHYL IMIDE 
(NCH,).! 


The hydriodides of methylated bases eliminate 
methyl iodide at 200°—300° in accordance with the 
equation R,NCHI,. HI-R,NH + CH,I; the iodide may 
be determined by Zeisel’s method (cf. p. 38 et seq.). 

The apparatus employed is iden- 
tical with that of Zeisel except 
the vessel in which the sub- 
stance is heated. This is shown 
C0» in Fig. 13, and consists of a 
double flask a 6 connected by 
means ofa cork with the vesselc. _ 
The method is modified accord- 
ing to whether one or more alkyl 
groups are linked to nitrogen, 
and, in the latter case, whether 
Fic. 13. these are to be determined suc- 
cessively; finally the presence of alkyloxy groups, in 
addition to methyl imide, demands special manipulation. 





(1) Determination with only one Alkyl linked to 
Nitrogen. 


The compound (0.15-0.3 gram) as free base, 
nitrate, or haloid salt is placed in the flask a with 





1J. Herzig and H. Meyer, B, 27, 319. M. 15, 613; 16,599; 18, 
379: 


DETERMINATION OF THE AMINO GROUP, ETC. I1I5 


sufficient hydriodic acid (sp. gr. = 1.68 — 1.72) to 
fill the vessel c to the mark de; the object of this is to 
retain any volatile basic compounds which might be 
carried over by the carbonic anhydride. In addition 
to the acid, the flask a also contains ammonium iodide 
in quantity equal to 5-6 times that of the substance em- 
ployed. The vessel C is connected directly with the 
condenser (Figs. 2, 3, 5, pp- 39, 40, 42); it should con- 
tain a little red phosphorus, if much iodine is liberated 
in a, as is usually the case when nitrates are employed. 
The flask 4 is filled with asbestos, a little of which is 
also placed in a to facilitate the boiling. A more rapid 
current of carbonic anhydride is used than in the de- 
termination of methoxyl, so as to remove the methyl 
iodide as quickly as possible and prevent its entering 
into combination with the other compounds produced, 
consequently two absorption flasks with silver nitrate 
must always be employed. The heating is done by 
means of a sand-bath of copper with a sheet-iron bot- 
tom; it is divided into two equal portions by a par- 
tition, and is of such a shape as to permit the flasks 
being immersed in the sand up to the line fg. The 
flask a is first heated, carbonic anhydride being passed 
through the apparatus; a portion of the acid distils into 
6 and some intoc. Gradually the second chamber of 
the bath is filled with sand, and 4 then directly heated. 

All the acid soon accumulates in c, the carbonic 
anhydride bubbling through it whilst the flask a con- 
tains only the hydriodide of the base. The commence- 
ment of the decomposition is indicated by a turbidity 
in the silver nitrate solution, and it occurs soon after 
the acid has been expelled from the flask 6. The re- 


116 RADICLES IN CARBON COMPOUNDS. 


mainder of the experiment is carried out exactly as in 
the methoxyl determination. 


(2) Determination with two or more Alkyl Groups 
linked to Nitrogen. 


This is carried out in the manner described on 
p. 114. When the operation is completed the appa- 
ratus is allowed to cool in a current of carbonic 
anhydride, ¢ is detached from the condenser, and by 
cautious tilting the acid poured from it back to 34, 
whence it will pass spontaneously toa. A fresh quan- 
tity of silver nitrate is placed in the absorption flasks, 
and the apparatus is ready to heat again. The opera- 
tion is repeated until the quantity of silver iodide ob- 
tained is equivalent to an amount of alkyl weighing 
less than 0.5 per cent of the substance employed. It. 
is important to conduct the determinations at the low- 
est possible temperature, and therefore a thermometer 
is placed in the sand-bath which is never allowed to 
exceed, by more than 40°, the temperature (200°-2 50°) 
at which the silver nitrate solution first becomes turbid. 
When several alkyl groups are present, it is advisable 
to use more ammonium iodide than otherwise, about 5 
grams in a, and 2-3 grams in 4. Each decompositior 
requires some two hours for completion, and three 
treatments are amply sufficient even though the com- 
pound contains three or four alkyls. 


DETERMINATION OF THE AMINO GROUP, ETC. I17 


(3) Successtve Determination of the Alkyl Groups. 


The alkyl groups may be successively eliminated 
from feebly basic compounds such as 
caffeine or theobromine. In place of 
the vessel previously employed (Fig. 
13), the substance is heated in one 
of the shape shown in Fig. 14. It is 
immersed in a sand-bath to the mark 
ab; after heating,the acid is allowed 
to flow back to the flask, a little am-_ 
monium iodide is added, and the 
heating repeated,—the operation be- 
ing performed a third time, with the 
addition of more ammonium iodide, Fic. 14. 
if three alkyl groups are present. 











(4) Determination of Methyl Imide in Presence of 
Methoxyl. 


The methyl imide may be determined in presence of 
methoxyl by heating the hydriodide alone in the flask 
a (Fig. 13); it is, however, preferable to add to it hy- 
driodic acid (10 cc), and heat the flask in an oil- or 
glycerol-bath so that scarcely any distils over into 3. 
When the operation is ended, which is indicated by the 
silver nitrate solution becoming clear, the temperature 
is raised, and the acid distilled off until only so much 
remains in @ as is usually employed for the methyl 
imide determination (p. 114). During the distillation 
the silver nitrate solution remains quite clear, and 
the methoxyl determination is completed. A fresh 
portion of silver nitrate is taken, the excess of acid re- 


118 RADICLES IN CARBON COMPOUNDS. 


moved from 4 and c, ammonium iodide added, and the 
methyl imide determination commenced in the manner 
described on p. I14. 


(5) General Remarks on the Method.' 


The purity of the hydriodic acid and ammonium 
iodide must be ascertained by means of a blank ex- 
periment (cf. p. 41). 

The method is applicable to all compounds which 
can form a hydriodide, even though this may not be 
capable of isolation, and accurate results are obtained 
by the use of any salt or double salt which is not ex- 
plosive and does not contain sulphur. Quantitative 
results are also obtained in the case of many com- 
pounds, such as z-ethylpyrroline, methylcarbazole, and 
dimethylparabanic acid, which do not form salts. Cer- 
tain substances containing the group CO.N.NCH, elimi-— 
nate the CH, almost as readily as methoxy] derivatives,’ 
this is especially the case with 1-phenyl-4-methylani- 
linourazole. In such circumstances therefore failure of 
a compound to react with hydriodic acid at the lower 
temperature indicates the absence of methoxyl, but 
the converse does not apply without further investi- 
gation. The limits of error lie between + 3 and — 15 
per cent of the total alkyl, consequently the presence 
or absence of one such group can only be determined 
with certainty when the theoretical difference in com- 
position for one alkyl exceeds 2 per cent, or, in other 





1J. Herzig and H. Meyer, M. 18 (1897), 379. Journ. Chem. Soc, 74, 


(1898), i. 53. 
2M. Busch, B. 35 (1902), 1565. 


_— 


DETERMINATION OF THE AMINO GROUP, ETC. IIQ 


words, when the molecular weight of the original 
methylated compound is less than 650. 

In considering the results obtained it is necessary to 
observe the colour of the silver iodide; should this be 
dark or gray instead of yellow, the error is almost 
always positive. 


100 parts AgI = 6.38 parts of CH,,. 


DETERMINATION OF ETHYL IMIDE (NC,H,). 


The method! of determination is exactly the same as 
that described for methyl imide (p. 114 et seq.). 100 
parts Ag] = 12.34 parts of C,H,. 


DIFFERENTIATION OF THE METHYL IMIDE 
AND BTHYE IMIDE: GROUFS: 


The method of determination by means of the alkyl 
iodides does not, as a rule, distinguish between ethyl 
imide and methyl imide; in doubtful cases it is neces- 
sary to distil a considerable quantity of the hydriodide 
of the base, and purify and identify the alkyl iodide 
which is evolved. A second method consists in distil- 
ling the base with potassium hydroxide, evaporating 
the distillate to dryness with hydrochloric acid, separat- 
ing the organic hydrochlorides from ammonium chlo- 
ride by means of absolute alcohol and chloroform, and 
converting the former into picrates, chloroplatinates, 
etc., which may then be identified; the method must, 
however, be used with caution, as it may lead to errone- 
ous results. 





1 J. Herzig and H. Meyer, B. 27, 319. M. 15, 613; 16, 599. 
2 Ciamician and Boeris, B. 29, 2474. 


CHAPTER V. 


DETERMINATION OF THE DIAZO GROUP (R.N:N); OF 
THE HYDRAZIDE RADICLE (NH. NH,); OF THE NITRO- 
GROUP (NO,); OF THE I0DOSO-tROUP (10); OF THE 
IODOXY-GROUP (I0,); OF THE PEROXIDE GROUP 


Ps 
CK d ; IODINE NUMBER. 
DETERMINATION OF THE DIAZO GROUP 
(R.N:N.R). 


The aliphatic and aromatic diazo-compounds (diazo- 
nium derivatives) are differently constituted, hence the | 
methods adapted for their determination are not 
identical. 


N 
(A) Aliphatic Diazo-compounds (C—CHC 4). 


The following methods are employed:' 

(1) Zttration with todine. 

(2) Analysts of the todo-derivatives. 

(3) Determination of the nitrogen in the wet way. 


(1) DETERMINATION OF THE NITROGEN BY TITRA- 
TION WITH IODINE. 


This reaction takes place in accordance with the 
equation CHN,.COOR + I,— CHI,,.COOR + N,. 


1 Curtius, J. pr. 146, 422. 





I20 


DETERMINATION OF THE DIAZO GROUP, ETC. I2I 


Rather more than the theoretical quantity of iodine 
is accurately weighed, dissolved in absolute ether, and 
added, by means of a burette, to a known quantity of 
the diazo-compound also in ethereal solution; the end 
of the reaction is indicated by a sharp change in the 
colour of the diazo-compound from lemon yellow to 
red; towards the conclusion of the titration the reac- 
tion is facilitated by warming the liquid on the water- 
bath. The excess of iodine solution is run into a 
tared flask, the ether cautiously removed, and the 
residue weighed. Unless the compound employed is 
in a high state of purity, the change of colour in the 
liquid takes place long before all the nitrogen has 
been expelled. 


(2) ANALYSIS OF THE IODINE DERIVATIVE. 


The iodine in the iodo-compound may be deter- 
mined in the ordinary manner, or the following simpler 
method, first used in the investigation of diazoaceta- 
mide,! may be employed. A weighed quantity of 
the substance is placed in a tared beaker, dissolved in 
a little absolute alcohol, and iodine added until a per- 
manent red coloration is obtained. The alcohol is 
volatilized on the water-bath, the excess of iodine 
removed by cautious heating, and the crystalline resi- 
due weighed. In this case, also, the compound em- 
ployed must be pure. 


(3) DETERMINATION OF THE NITROGEN IN THE 
WET WAY. 


On account of the great volatility of the aliphatic 
ethereal diazocarboxylates the method of nitrogen 





1 Curtius, J. pr. 146, 423. 


122, RADICLES IN CARBON COMPOUNDS. 


determination described on p. 95 cannot be employed. 
This difficulty is overcome! by the use of the apparatus 
i shown in Fig. 15. Aisa 

E a ; large gas cylinder contain- 
|. ing water, va capillary tube, 

| the upper open end of 
A B which rises a little above 


Be the level of the water in 
i A. E is a gas-measuring 
Ke tube, B a small condenser 

fitted to the little flask C 

by means of a rubber stop- 
per; through this a platinum wire also passes. Itis bent 
in the manner shown and carries a glass-stoppered vessel 
such as is employed in vapor density determinations. 
The flask C is partially filled with well boiled, highly 
dilute sulphuric acid, the compound (about 0.2 gram) | 
weighed into the small vessel s, and the apparatus 
fitted together air-tight. When the air in the appa- 
ratus is in equilibrium with the atmosphere, which can 
readily be observed if a drop of water is placed in 7, 
the volume of air in the eudiometer tube is read off, 
and the temperature noted. The vessel s is now 
dropped into the acid, which is gradually heated to 
boiling; the decomposition is completed in a few min- 
utes. The apparatus is allowed to cool completely, 
the level of water in and outside the tube £& adjusted, 
and the volume, temperature, and pressure noted; the 
difference in volume from the previous reading gives 
the quantity of nitrogen evolved. As a rule the 


























Fic. 15. 





1 Curtius, J. pr. 146, 417. 


DETERMINATION OF THE DIAZO GROUP, ETC. 123 


atmospheric pressure does not materially change dur- 
ing the experiment. 

Compounds containing an amino as well as a diazo- 
group, such as diazoacetamide, may be decomposed 
by means of dilute hydrochloric acid; after the evolu- 
tion of nitrogen is completed the ammonium chloride 
in the flask c may be precipitated with hydrochloro- 
platinic acid and the amino and diazo nitrogen thus 
separately determined in one operation. 


(B) Aromatic Diazo Compounds. (Diazonium Deriva- 
tives C.N.OH.) 


The diazo group in aromatic compounds is usually 
determined by the preceding method! (3), p. 121, but 
it is preferable to employ a Lunge’s nitrometer and 
40 per cent sulphuric acid.” Sulphuric acid, sp. gr. = 
1.306, has a vapor tension of 9.4 mm at 15°.° 

A modification consists in dissolving the diazonium 
salt in ice-water, adding hydrochloric acid, and dis- 
placing the air by means of carbonic anhydride while 
the solution is in a freezing-mixture. Cuprous chlo- 
ride is then added, and the liquid gradually heated 
to boiling. The necessary correction for dissolved 
air is ascertained by a blank experiment.‘ On 
account of the action of acids in producing intra- 





1 Knoevenagel, B. 23, 2997. v. Pechmann and Frobenius, 4rd. 27, 
706. 

2 Bamberger, Jéid. 27, 2598. 

3 Regnault. 

4H. Goldschmidt and A, Merz, /éid. 29, 1369 ; 30, Hl A, Hautzsch, 


Ibid. 33 (1900), 2159. 


124 RADICLES IN CARBON COMPOUNDS. 


molecular rearrangement of diazonium derivatives, it is 
desirable to reduce the time required to expel the air 
from the apparatus and to avoid the necessity for work- 
ing at 0°. The apparatus shown in Fig. 16 is de- 











Fic. 16. 


signed to accomplish this. It has been used with great 
success for the determination of diazo nitrogen in 
diazoamino derivatives. It consists of a thin-walled 
test tube 10-12 X31 cm. The tubes are inserted flush 
with the rubber stopper. The substance is placed in 
the tube, the leg of the funnel, which is drawn toa 
fine point, is filled with recently boiled water. The 
tube d is connected with an air-pump, ¢ with a car- 
bonic anhydride apparatus, and a with a eudiometer; 4 is 
a three-way cock; a is closed, the apparatus exhausted, 
carbonic anhydride introduced, and the exhaustion 
and introduction of carbonic anhydride repeated twice 
more. The air in ais then expelled by a very rapid 





* 1H. Mehner, J. pr. 63 [2] (1901), 304. 


DETERMINATION OF THE DIAZO GROUP, ETC. 125 


current of carbonic anhydride, 4 closed, the funnel 
filled with conc. hydrochloric acid, and enough | 
introduced into the test-tube to fill it one fifth. The 
liquid is now rapidly heated to boiling and the evolu- 
tion of nitrogen takes place speedily. When the ex- 
periment is completed, the greater part of the gas in 
the apparatus is expelled by means of boiled water, 
the remainder by carbonic anhydride. No aminoazo 
derivatives are produced, the method is very rapid, and 
at least as accurate as that of Dumas. 


DETERMINATION OF THE HYDRAZIDE 
GROUP (NH.NH)). 


Either the oxidation or iodometric method may be 
employed. 


(1) OXIDATION OF HYDRAZIDES.!” 


Boiling Fehling’s solution hydrolyses acid hydra- 
zides, and oxidizes the resulting phenylhydrazine, the 
nitrogen of which is evolved quantitatively and deter- 
mined by the method described on p. 74. The com- 
pound is dissolved, if possible, in water or alcohol; 
hydrazides which do not dissolve are weighed into a 
small stoppered vessel which is fixed mouth downwards 
in the hole of the stopper otherwise occupied by the 
funnel A, Fig. 11, p. 75, and is dropped into the boiling 
solution by means ofa glass rod of the same volume. 
Insoluble compounds may also be treated according to 





1H. Strache and S. Iritzer, M. 14, 37. Holleman and de Vries, 
Rec. 30, 229: De. Vries, B.-27, 1521-28. 201%8.. Peteren, 7. An: 


5) 2. 


126 RADICLES IN CARBON COMPOUNDS. 


the following method:! 100 cc Fehling’s solution, 
and 150 cc alcohol, with a few fragments of porce- 
lain, are placed in a 500 cc flask fitted with a doubly 
bored rubber stopper. In the one hole the tube con- 
taining the weighed substance is placed, through the 
other the end of an inclined condenser passes. The 
contents of the flask are boiled, and the open end of the 
condenser connected with a bent tube terminating in 
a short leg which dips below water. When no more 
air is expelied,a measuring vessel full of water is placed 
over the end of the tube, and the vessel with the sub- 
stance pressed into the flask by means of a rod. Con- 
tinued boiling for a short time suffices to liberate all 
the nitrogen. 

In some cases it is desirable to recover the acid on 
account of its rarity, or to remove it in order to facili- 
tate the determination, as in the case of stearic acid, - 
the potassium salt of which causes the liquid to froth 
over. This can be accomplished, if the acid is spar- 
ingly soluble in water or dilute hydrochloric acid, by 
boiling the hydrazide with concentrated hydrochloric 
acid, during several hours; the solution is made up to 
100 cc, the organic acid removed by means of a dry 
filter, the first few drops of the filtrate rejected, and 50 
cc of the remainder taken for the determination. This 
method of hydrolysis does not distinguish between 
hydrazides and hydrazones, as the latter are also acted 
upon by hydrochloric acid. Ortho- and paratolyl- 
hydrazides are oxidized in the same manner as phenyl- 
hydrazides, so that the method is also applicable to 
them.?. 





1H, Meyer, M. 18, 404. 2M. 14, 38. 


DETERMINATION OF THE DIAZO GROUP, ETC. 127 


Hydrochloroplatinic acid oxidizes hydrazine hydro- 
chloride in accordance with the equation 


N,H,.2HCI + 2H,PtCl, oN, +- 10oHCl + 2PtCl; 


the evolved nitrogen is determined by the method 
described on p. 121.’ 

Hydrazine salts may be titrated by potassium per- 
manganate in presence of sulphuric acid, provided the 
concentration of the latter is 6-12 per cent.* The re- 
action is represented by the equation 


17N,H, + 130-13H,0 + 14NH, + I0N,. 


(2) IODOMETRIC METHOD.’ 


Phenylhydrazine and iodine react in accordance with 
the following equation: 


C,H,NH.NH, + 21,>3HI + N, + C,H,I. 


The interaction is quantitative, in highly dilute solu- 
tion, with iodine present in excess. The determination 
is made by adding to a known volume of N/Io iodine 
solution, the highly dilute solution of the base or its 
hydrochloride, obtained by hydrolysis, p. 109; the 
excess of iodine is then titrated in the ordinary 
manner. 

In presence of dilute sulphuric acid, iodic acid oxi- 
dizes phenylhydrazine, and this reaction may also be 
employed for the determination.. The strength of the 
iodic acid solution is ascertained by means of sulphurous 
acid of known titre; it is then added, in excess, to the 





1 Curtius, J. pr. 147, 37. * Petersen, \Z. An; 6.3. 
5 E. v. Meyer, J. pr. 149, 115. 


128 RADICLES IN CARBON COMPOUNDS. 


highly dilute solution of phenylhydrazine and sulphuric 
acid, and the mixture again titrated. 

Arsenic anhydride and phenylhydrazine react in ac- 
cordance with the equation 


As,O, + C,H,NH.NH,-N, t H,O + C,H,OH -+- As,QOs3, 


Two methods of analysis have been worked out based 
on this reaction. (1) Phenylhydrazine hydrochloride 
is agitated with arsenic acid solution in excess, and the 
liquid titrated with a uranium salt, which is also em- 
ployed to determine the content of arsenic acid in the 
original solution. (2) After treatment with arsenic 
acid as before, the arsenious acid produced is deter- 
mined by means of iodine. The following solutions 
are required: 

Lodine (N/10); 

Sodium hydroxide (200 grams in 1 liter) ; 

Sodium hydrogen carbonate (cold saturated solution) ; 
— Starch solution (freshly prepared) ; 

Arsenic acid solution (125 grams arsenic anhydride 
dissolved in hot water (450 cc) and conc. hydro- 
chloric acid (150 cc), cooled, filtered, and made up to 
1 liter with glacial acetic acid). 

The phenylhydrazine hydrochloride, or tree base, 
(0.2 gram) is mixed with the arsenic acid solution (60 
cc), and the liquid boiled steadily by the help of a 
small platinum spiral in a reflux apparatus for 40 min- 
utes. Water (200 cc) is added, and the liquid neu- 
tralized with sodium hydroxide, phenolphthalein being 
used as indicator. It is now made just acid with 
hydrochloric acid, mixed with sodium hydrogen car- 


DETERMINATION OF THE. DIAZO GROUP, ETC. 129 


bonate solution (60 cc), and titrated with iodine in the 
usual Manner. 1 part As.O, = 0.5454 parts'‘C.ri No) 

To the above methods may be added the titration 
of phenylhydrazine with hydrochloric acid; rosolic acid 
or methyl-orange is used as indicator, and tolerably 
accurate results are obtained.’ 


DETERMINATION OF THE NITRO-GROUP 
(NO,). 


(A) Titration Method.’ 


Organic nitro-compounds are reduced to amino- 
derivatives by the action of stannous chloride, in 
presence of hydrochloric acid, in accordance with the 
equation 


R.NO, + 3SnCl, + 6HCIOR.NH, + 3SnCl, + 2H,O; 


the unchanged stannous chloride is determined by 
titration, and, from the quantity which has reacted, 
the number of nitro-groups in the original compound 
may be ascertained. Solution of iodine, or of potas- 
sium permanganate, is employed for the titration—the 
latter when much colour is developed. The method is 
inapplicable to trinitrophenol or nitronaphthalene.+ 





1H. Causse, Bull. 19 [3], (1898), 147. 

? Strache and Iritzer. 

8H, Limpricht, B. 11, 35; Spindler, Ann. 224, 288. 

‘Jenssen, J. pr. 78, 193. S. W. Young and R. E, Swain, J. Am, 
(1897), 19, 812-814. Journ, Chem, Soc, (1898), 74, ii, 186. P. Alt- 
mann, J. pr. (1901) 63 [2], 370. 


130 RADICLES IN CARBON COMPOUNDS. 


Reagents Required. 


(1) Stannous Chloride Solution. Tin (150 grams) is 
dissolved in concentrated hydrochloric acid, the clear 
liquid decanted, mixed with concentrated hydrochloric 
acid (50 cc), and diluted to 1 liter. 

(2) Sodium Carbonate Solution. Anhydrous sodium 
carbonate (90 grams) and sodium potassium tartrate 
(120 grams) are dissolved in water and diluted to 1 liter. 

(3) lodine Solution. Iodine (12.54 grams) is dis- 
solved in potassium iodide solution, and the liquid made 
up to I liter, it will then be approximately N/10; if 
exactly so I cc = 0.0059 gram Sn = 0.0007655 gram 
NO, 

(4) Starch Solution. This must be dilute, recently 
prepared, and filtered. 

Potasstum Permanganate Solution. It should be 
N/1o, and may be used instead of the iodine, its 
strength being determined by means of iron. 


(I) Method of Determination for Non-volatile 
Compounds. 


After the titre of the stannous chloride has been 
ascertained, the nitro-compound (about 0.2 gram) is 
placed in a 100 cc glass-stoppered flask, stannous 
chloride solution (10 cc) added, and the liquid warmed 
during thirty minutes. When cool, the mixture is di- 
luted to the mark, and, after shaking, 10 cc transferred 
to a beaker by means of a pipette; a little water is 
added, then the sodium carbonate solution, until the 
precipitate which first forms is wholly dissolved; after 
the addition of a little starch,the iodine solution is run 
in until a permanent blue colouration is produced. 


DETERMINATION OF THE DIAZO GROUP, ETC. 131 


The results of the analysis are calculated according 
to the formula NO, = (a — 6).0.0007655 gram, where 
a= the number of cc of iodine solution equivalent to 1 
cc of the stannous chloride solution, and =the number 
of cc of iodine solution required in the determination. 

If it is desired to use the potassium permanganate, 
10 cc of the acid liquid, withdrawn as described above, 
is boiled with ferric chloride, and the ferrous chloride 
produced is determined in the ordinary manner. 


(Il) Modified Method for Volatile Compounds. 


Volatile nitro-compounds are weighed in a test-tube 
about 30 cm by 8 mm, closed with a cork; the cork 
is removed, and the tube, together with the stannous 
chloride, placed in a second larger one, 20 cm by 
13-15 mm, which is then sealed. The larger tube 
may be of thin-walled, readily fusible glass, as it will 
only be subjected to a very slight pressure. The tube 
is heated in the water-bath during 1-2 hours, and well 
shaken occasionally; it is then cooled, the contents 
completely washed into a 100-cc graduated flask, and 
treated in the manner described in the preceding sec- 
tion. The use of a sealed tube is sometimes advisable 
in the case of non-volatile compounds with which low 
results may be obtained by heating in the stoppered 
bottle. 

Many aromatic nitro-compounds evolve nitrogen 
quantitatively when treated with phenylhydrazine at or 
adlittle-above- 100°, (Ch pe 192.) 

R.NO, + 3C,H,NH.NH? 

— R.NH, + 3C,H, + 2H,O + 3N,. 
1R, Walter, J. pr. 53 [2], (1896), 437. 





132 RADICLES IN CARBON COMPOUNDS. 


(B) Diazo Method.' 


Should the preceding method fail to give decisive 
results the nitro-compound must be reduced to the 
amino-derivative and this treated in the manner de- 
scribed on pp. 95, 103. As an example, metanitro- 
benzaldehyde may be converted into metachloro- 
benzaldehyde by one operation.* It is dissolved in 
concentrated hydrochloric acid (6 parts), stannous 
chloride (4.5 parts) added, and after the reduction, 
without precipitating the tin, it is mixed with the cal- 
culated quantity of sodium nitrite and an equal weight 
of finely divided copper. 


DETERMINATION OF THE NITROSO (NO) 
GROUP.’ 


The method depends on the fact that, under suit-. 
able conditions, simple nitroso-compounds react with 
phenylhydrazine in accordance with the equation: 


R.NO + C,H,NH.NH, >RN + H,O + C,H, + N,. 


The apparatus employed is shown in Fig. 17, p. 133. 
The substance (0.1-0.2 gram) is weighed into the 300 
cc flask R, and dissolved in glacial acetic acid (20-30 
cc). The apparatus is then fitted together,and the air 
displaced by a slow stream of carbonic anhydride. This 
may require several hours. When most of the air has 
been removed from the flask and condenser,the car- 
bonic anhydride is diverted by means of the three-way 
cock P through the funnel so as to remove the air from 





1 Gattermann, B. 23, 1222. 2 Gattermann, Joc. cit. 
3 R. Clauser, B. 34 (1901), 891. 


DETERMINATION OF THE DIAZO GROUP, ETC. 133 


its lower part. The bulbs, filled with potassium hy- 
droxide solution (2:3) are then attached, and, if the air 
has been completely expelled, 4—5 times the theoreti- 


EEE 


= 












































Se 


Fig. 17. 





cal quantity of phenylhydrazine, dissolved in concen- 
trated acetic acid (30-40 cc), is placed in the funnel 
and the flask gently warmed. By means of the cock 
P sufficient pressure may be obtained in the funnel for 
its contents to flow into the flask. The reaction usually 
- requires 10 minutes for completion; but in the case of 


134 RADICLES IN CARBON COMPOUNDS. 


substances sparingly soluble in acetic acid, such as a@,- 
nitroso-qa,-naphthol, the heating is continued for 30 
minutesormore. The nitrogen collected in the absorb- 
tion apparatus by the stream of carbonic anhydride, is 
transferred to a measuring vessel, and allowed to stand 
over concentrated potassium hydroxide solution con- 
taining a few drops of benzene (vzde p. 77). The results 
are calculated by means of the formula 
3000.sV.(4— @w)  K.V(d —@) 
760.28.(1 + at)g— g.(1 + at)” 
P = per cent of nitroso groups in the substance; V 
the cc nitrogen obtained; w =the sum of the tension 
of water and benzene at the temperature ¢; and g the 
3000.5 
760 4 28” 
where S = weight of I cc nitrogen at NTP. The 
results are usually accurate to 0.5 per cent of P. The 
method has not yet been tested with complex com- 
pounds such as nitrosamines, polynitroso-, and iso- 
nitroso-derivatives and esters of nitrous acid. 


Ps 








grams of substance taken. K is the constant 


DETERMINATION OF THE IODOSO- (IO) 
AND IODOXY- (I0,) GROUPS. 


Iodoso- and iodoxy-compounds in presence of glacial 
acetic, of hydrochloric acid, or of dilute sulphuricacid, 
liberate from potassium iodide an amount of iodine 
equivalent to their content of oxygen; one molecule of 
the former therefore liberates two, and of the latter 
four atoms of iodine. For the determination, the sub- 
stance is heated on the water-bath during four hours 
with acidified potassium iodide solution in a sealed tube 


DETERMINATION OF THE DIAZO GROUP, ETC. 135 


from which the air has been expelled by carbonic 
anhydride. The compound may also be digested on 
the water-bath with concentrated potassium iodide 
solution, glacial acetic acid, in fairly large quantity, 
and dilute sulphuric acid.2, When the reaction is com- 
pleted the liquid is titrated with N/1o sodium thiosul- 
phate solution; no indicator is required. Whenever 
hydrochloric acid or sulphuric acid has been employed 
in the reduction the iodide, which is produced, always 
retains some iodine in solution, hence, during the 
titration, it is mecessary to warm and shake the 
liquid until this has all been acted upon by the 
thiosulphate. The oxygen percentage content of the 
iodoso- and iodoxy-compounds is given by the formula 
0.8.¢.100 c ? : 

= SaaS 0.08 —, where s is the weight of the 
compound taken and c the number of cc of N/1o sodium 
thiosulphate employed. 


DETERMINATION OF THE PEROXIDE GROUP 


The oxygen of the acyl superoxides may be deter- 
mined by means of stannous chloride in acid solution.® 
A known quantity of the peroxide is heated, during 
about five minutes, in an atmosphere of carbonic 
anhydride, with a measured volume of a titrated, acidi- 


1'V. Meyer and Wachter, B. 25, 2632. P. Askenasy and V. Meyer, 
Ibid, 26, 1355, ef seq. 

? Willgerodt, /dzd. 25, 3405, et seq. 

’ Pechmann and Vanino, /ézd, 27, 1512. 





136 RADICLES IN CARBON COMPOUNDS. 


fied stannous chloride solution. When the liquid is 
clear,the remaining stannous chloride is determined by 
means of N/1o iodine solution. The substance may 
also be treated with glacial acetic acid and potassium 
iodide solution until a clear liquid is obtained and 
the liberated iodine titrated with sodium thiosulphate. 
The results should be corrected by means of a blank 
experiment.! 


THE IODINE NUMBER.? 


This value expresses the quantity of iodine absorbed 
by one hundred parts of the substance, usually a fat or 
higher aliphatic acid. The acids of this series, such 
as oleic acid, ricinoleic acid, linoleic acid, and linolenic 
acid, as well as their glycerides, absorb, the first two, 
the others four and six atoms of iodine, bromine, or 
chlorine respectively, whilst the corresponding saturated 
compounds, under similar circumstances, are scarcely 
affected. The reaction is carried out at the ordinary 
temperature, the substance being mixed with alcoholic 
iodine and mercuric chloride solutions.? The organic 
products are chloro-iodine additive compounds, some 
of which have been isolated and characterized. The 





1A, Baeyer and O, -Villiger, B. 34 (1901), 765. 

? Benedikt, ‘‘ Analyse d. Fette und Wachsarten,”’ III. Edition, p. 148. 
Allen, ‘‘ Commercial Organic Analysis,”’ vol. II, 3d Edition, J. Lewko- 
witsch, ‘‘ Chemical Analysis of Oils, Fats, and Waxes” (1902), and 
‘‘Laboratory Companion to Fats and Oils Industries” (1901), The 
former work deals chiefly with methods, the latter with ‘ constants,” 
E, Hopkins, ‘‘ Oil Chemist’s Handbook ” (1900), is smaller and contains 
data and methods. 

§’ Hibl, Dingl. 253, 281. 

*R. Henriques and H, Kunne, B. 32, 380. 


DETERMINATION OF THE DIAZO GROUP, ETC. 137 


method is extensively employed: in the technical in- 
vestigation of fats, oils, waxes, resins, ethereal oils, 
caoutchouc, etc., and is sometimes useful for scientific 
purposes, hence a brief description of the details of 
analysis is given here. 


Reagents. 


(1) Lodine Solution. Iodine (25 grams), and mer- 
curic chloride (30 grams) are separately dissolved in 
95 per cent alcohol (500 cc), free trom fusel oil. The 
mercuric chloride solution is filtered, if necessary, and 
the liquids mixed. The mixing must precede the use 
of the solution by 6-12 hours as, during this period, 
the titre rapidly changes. Instead of this a solution 
of iodine monochloride, or iodine bromide in pure 
glacial acetic acid may be used; with care it gives 
results identical with the alcoholic solution described 
above, and is greatly superior to it in stability.' 

(2) Sodium Thtosulphate Solution. The crystallized 
salt (24 grams) is dissolved in water, and diluted to one 
liter. It is standardized in the following manner:? 
Potassium bichromate (3.8740 grams) is dissolved in 
water, diluted to one liter, and 20 cc of the liquid 
transferred to a stoppered bottle containing 10 cc of 
potassium iodide solution (10 per cent), and 5 cc hy- 
drochloric acid; the liberated iodine is then titrated in 
the ordinary manner by means of sodium thiosulphate, 
starch being used as indicator ; 1 cc of the above bichro- 
mate solution liberates 0.01 gram of iodine. 





1jJ. J. A. Wijs, B. 31 (1898), 750. J. Lewkowitsch, Analyst, 24 


(1899), 257. 
2 Volhard. 


138 RADICLES IN CARBON COMPOUNDS. 


(3) Chloroform. Its purity is determined by a blank 
experiment. 

(4) Potassium Iodide Solution. The salt is dissolved 
in ten parts of water. 

(5) Starch Solution. This must be clear and re- 
cently prepared. 


Method of Analysts. 


The substance (0.15-1.0 gram) is mixed with chlo- 
roform (about 10 cc) in a 500-800 cc flask provided 
with a well-fitting glass-stopper. When the com- 
pound has dissolved,the iodine solution (25 cc) is added 
by means of a pipette which must be manipulatéd so 
that equal quantities are delivered in each experiment. 
The flask is well shaken, and more chloroform added 
if needful; should the liquid become almost colourless - 
in a short time a second 25 cc of iodine solution is 
added, and this repeated, if necessary, until, after the 
expiration of two hours, the liquid appears dark brown. 
The mixture is now allowed to remain during twelve 
hours at the ordinary temperature in the dark; it is 
then thoroughly mixed with at least 20 cc of potassium 
iodide solution and 300-500 cc of water, and titrated 
with the sodium thiosulphate solution, the liquid being 
constantly agitated; when only a faint colour is visible 
in both the aqueous and chloroform solutions, starch 
is added and the titration completed. The production 
of a red precipitate of mercuric iodide, on the addition 
of water before the titration, indicates that too little 
potassium iodide has been employed, but this may be 
corrected by the immediate addition of more. A 


DETERMINATION OF THE DIAZO GROUP, ETC. 139 


blank experiment must always be made with 25 cc of 
the iodine solution,under exactly the same conditions 
as the test, and its titration must immediately precede 
or follow that of the actual determination. 

Useful information is sometimes given by the Zere- 
benthene number,‘ and the acetyl value.? 





1 J. Klimont, Ch. Ztg. (1894), No. 35, 37. Ch. R. (1894), 2, 2. 
2 J. Lewkowitsch, Analyst, 24 (1899), 319. 





APPENDIX. 


14! 


142 


APPENDIX. 


WEIGHT OF A CUBIC CENTIMETER OF HYDROGEN 
PERATURE OF 10°25°.’ 


The observed height of the barometer is reduced to 0° by 
and 20°-25° respectively. 





- Height of 
barom- 


to? C, 


mg 


17°C; > a tte 


mg mg 


r3°-C. 


mg 


ae, 


mg 


5 has C; 


mg 


16°C, 


mg 


mg 





0.07851 
0.07874 
0.07896 
0.07919 
0.07942 
0.07964 
0.07987 
0.08009 
0.08032 
0.08055 


0.08078 
0.08101 
0.08123 
0.08146 
0.08169 


0.08191 
0.08215 


0.08237, 
0.08259, 


0.08282 
0.08305 
0.08328 
0.08351 


0.08373 
0.08396, 


0.08419 
0.08441 
0.08464 
0.08487 
0.08510 
0.08533 
0.08555 
0.08578 
0.08601 
0.08624 


0.08646 





0.07816 
0.07839 
0.07861 
0.07884 
0.07907|0.07871 


0.07929 0.07893 
0. 7952/0. -O7917 
9.07975)0. peas 
aga tare 

54 07954 
0.08043 0.08007 
0.08065 0.08029 
0.08087 0.08052 
0.08110|0.08074 


0.07781 
0.07804 
0.07826 
0.07848 








0.08133 0.08097 


0.08156 0.08120 
0.08179'0.08142 
0.08201 0.08164 
0.08224/0.08187 


0.08246 


jeig208 
biecwesaats metal 
0.06291 


| 0.08255 
0.08314 0.08277 
0.08337|0.08300 
0.08360 0.08322 


os 0838200. -08344 
0. 08404 0.08368 
O. 08428, 0.08390 
Oo. 08450. 0.08413 


0.08472|0.08435 


0.08496 
0.08518 
0.08541 
0.08563 
0.08586 
0.08608 








0.08458 
0.08481 
0.08503 
0.08525 
0.08549 
0.08571 


0.07746 
0.07769 
0.07791 
0.07813 
0.07836 
0.07858 
0.07881 
0.07903 
0.07924 
0.07948 
0.07971 
0.07993 
0.08016 
0.08038 
0.08061 


0.08083 
0.08106 
0.08129 
0.08151 
0.08173 


0.08196 
0.08218 
0.08240 
0.08263 
0.08285 


0.08308 
0.08331 
0.08353 
0.08376 
0.08398 


0.08420 


0.08443 
0.08465 





| 
| 


0.08487 
0.08511 


0.08533 


0.07711 
0.07713 
0.07756 
0.07778 
0.07800 
0.07823 
0.07845 
0.07868 
0.07890 
0.07912 


0.07935 
0.07957 
0.07979 
0.08002 
0.08024 


0.08047 
0.08069 
0.08091 
0.08114 
0.08136 


0.08158 
0.08181 
0.08203 
0.08226 
0.08248 


0.08270 
0.08293 
0.08315 
0.08338 


0.08360, 


0.08382 
0.08405 
0.08428 
0.08450 
0.08473 


0.08495 





0.07675 
0.07697 
0.07720 
0.07742 
0.07774 
0.07787 
0.07809 
0.07832 
0.07854 
0.07876 
0.07899 
0.07921 
0.07943 
0.07965 
0.07987 
0.08010 
0.08032 
0.08055 
0.08077 
0.08099 


0.08122 
0.08144 
0.08166 
0.08189 
0.08211 


0.08234 
0.08256 
0.08278 
0.08301 
0.08323 


0.08389 
0.08412 
0.08434 
0.08466 


0.07639 
0.07661 
0.07684 
0.07706 
0.07729 


0.07750 
0.07772 
0.07795 
0.07817 
0.07840 
0.07862 
0.07884 
0.07907 
0.07929 
0.07951 


0.07973 
0.07995 
0.08018 
0.08040 
0.08062 


0.08084 
0.08106 
0.08129 
0.08151 
0.08173 


0.08195 
0.08218 
0.08240 
0.08262 


0.07603 
0.07625 
0.07647 
0.07670 
0.07692 
0.07714 
0.07736 
0.07759 
0.07781 
0.07803 
0.07825 
0.07847 
0.07869 
0.07891. 
0.07913 
0.07936 
0.07958 
0.07980 
0.08002 
0.08024 


0.08047 
0.08069 
0.08091 
0.08113 
0.08135 


0.08158 
0.08180 
0.08202 
0.08224 





0.08285 


0.08246 


0.08345, 
'0.08367 








0.08307 0.08269 
O. 08329, 0.08291 
0. -08352/0. .08313 
0.08374/0.08335 
0.08396,0.08357 


waa ka wi 





1A, Baumann, Z. ang. Ch, 1891, 210. 


UNDER A PRESSURE OF 700-770 mm AND AT 
(6 — @)0.089523 


Vekic ot Got 6.00360!) 


APPENDIX. 





). 


143 


A TEM- 


subtracting 1, 2, or 3 mm for the temperatures 10°-12°, 13°-19", 





18° C. 


mg 


19°C. 


mg 


mg 


mg 


22°: 


mg 


23°1G. 


mg 


24°.G: 


mg 


250 GC: 


mg 





0.07557 
0.07588 
0.07610 
0.07633 
0.07655 
0.07677 
0.07699 
0.07722 
0.07743 
0.07765 
0.07788 
0.07809 
0.07831 
0.07854 
0.07876 
0.07908 
0.07920 
0.07942 
0.07964 
0.07986 
0.08009 
0.08030 
0.08053 
0.08075 
0.08097 
0.08119 
0.08141 
0.08163 
0.08185 
0.08207 


0.08229 
0.08251 
0.08273 
0.08295 
0.08318 








0.07529 
0.07552 
O 07574 
0.07595 
0.07618 
0.07640 
0.07662 
0.07684 
0.07706 
0.07728 


0.07749 
0.07772 
0.07794 
0.07816 
0.07838 
0.07860 
0.07882 
0.07904 
0.07926 
0.07948 


0.07970 
0.07992 
0.08014 
0.08036 
0.08058 


0.08080 
0.08102 
0.08124 
0.08146 
0.08168 


0.08190 
0.08212 
0.08234 
0.08256 
0.08278 





ea tt 


0.08301 


0.07493 
0.07515 
0.07537 
0.07559 
0.07581 
0.07603 
0.07625 
0.07646 
0.07668 
0.07690 
0.07712 
0.07734 
0.07756 
0.07778 
0.07800 
0.07822 
0.07844 
0.07866 
0.07888 
0.07910 


0.07932 
0.07954 
0.07976 
0.07998 
0.08020 
0.08042 
0.08063 
0.08085 
0.08107 
0.08129 


0.08151 
0.08173 
0.08195 
0.08217 
0.08239 


0.07455 
0.07477 
0.07499 
0.07521 
0.07543 
0.07565 
0.07587 
0.07608 
0.07630 
0.07652 
9.07674 
0.07696 
0.07718 
0 07740 
0.07762 
0.07784 
0.07805 
0.07827 
0.07849 
0.07871 
0.07893 
0.07915 
0.07937 
0.07959] 
0 07981 


0.08002 





0.07417 
0.07439 
0.07461 
0.07483 
0.07505 
0.07527 
0.07548 
0.07570 
0.07592 
0.07614 
0.07635 
0.07657 
0.07679 
0.07701 


0.07723) 


0.07744 
0.07766 
0.07780 
0.07810 
0.07831 
0.07853 
0.07875 
0.07897 
0.07919 
0.07940 
0.07962 


0.08024 0.07984 


0.08046: 
0.08068 
0.08090 


0.08112 
0.08134 
0.08155 
0.08177 
0.08199 





0.08261 








0.08221 


0.08006 
0.08028 
0.08050 


0.08071 
0.08093 
0.08115 
0.08137 
0.08158 


0.08180 


0.07380 
0.07401 
0.07422 


0.07444 
0.07466 


0.07487 
0.07509 
0.07531 
0.07553 
0.07574 
0.07596 
0.07618 
0.07640 
0.07661 
0.07683 


0.07705 
0.07727 
0.07748 
0.07770 
0.07792 
0.07813 


0.07340 
0.07362 
0.07383 
0.07405 
0.07427 
0.07449 
0.07470 
0.07492 
0.07513 
0.07535 
0.07550 
0.07577 
0.07609 
0.07621 
0.07643 








0.07300) 
0.07322) 
0.07344) 
0.07366, 
0.07387 
0.07409 
0.07431 
0.07452 
0.07473 
0.07495 
0.07516 
0.07538 
0.07560 
0.07582 
0.07604 


0.07665 (0.07624 
0.07687 0.07646 
0.07708 0.07668 
0.07730/0.07689 
0.07752|0.0771I 


0.07774 





0.07835 
0.07857) 
0.078 79) 
0.07900 
0.07922! 
0.07944 
0.07966 
0.07987 
0.08009 
0.08031 
0.08052 
0.08074 
0.08096 
0.08118 








0.08139 


0.07795 
0.07817 
0.07838 
0.07860 
0.07881 





0.07732 
0.07754 
0.07776 
0.07797 
0.07819 


0.07840 


0.07903 0.07862 
0.07925 0.07883 
PoE O:071905 
OTIS 87927 
007990 0;07949 
0.08012'0.07970 
0.08033/0.07992 
0.0805 5/0.08013 
0.08076/0.08034 


0.08098 0.08056 





Height of 
barom- 
eter. 


B 
B 





8 





144 


APPENDIX. 


TENSION OF AQUEOUS VAPOR. 










































































or, mm o? C, mm 

10.0 9-165 18.0 15.357 

10.5 9-474 18.5 15.845 

II.O 9-792 19.0 16.346 

11.5 10.120 19.5 16.861 

12.0 10.457 20.0 17.391 

12.5 10.804 20.5 17.935 

13.0 11.162 21.0 18.495 

13.5 II.530 21.5 19.069 

14.0 11.908 22.0 19.659 

14.5 12.298 22:5 20. 265 

15.0 12.699 23.0 20.888 

15.5 _- 13.112 23.5 21.528 

16.0 13.536 24.0 22.184 

16.5 13-972 24.5 22.858 

17.0 14.421 25.0 23-550 

17.5 14.882 
TABLE FOR THE VALUE OF . a=I—a=ggg.! 

I000 — a 
° I | 2 3 4 5 6 7 8 9 

00 | 0.0000 | OITO | 020 | 030 | 040 | 050 | O60 | O71 | O81 | OgI 
Or Tot. -|_1115 | 322 1-198 | 142°) 1§2- 1 163:| 173 | 183 1.204 
02 204 | 215 | 225 | 235 | 246 | 256 | 267 | 278 | 288 | 299 
03 309 | 320 | 331 | 341 | 352 | 363 | 373 | 384 | 395 | 406 
04 417 | 428 | 438 | 449 | 460 | 471 | 482 | 493 | 504 | 515 
05 526 | 537 | 549 | 560 | 571 | 582 | 593 | 605 | 616 | 627 
06 638 | 650 | 661 | 672 | 684 | 695 | 707 | 718 | 730 | 741 
07 753 | 764 | 776 | 788 | 799 | 811 | 823 | 834 | 846 | 858 
08 | 0.0870 | 881 | 893 | 905 | 917 | 929 | 941 | 953 | 965 | 977 
0g 989 |*oor |*o13 |*o25 |*038 |*o50 |*062 |*074 |*087 |*og9 
IO | O.I1IX | 124 | 136 | 148 | 15r | 173 | 186 | 198 | 211 | 223 
1I 236 | 249 | 261 | 274 | 287 | 299 | 312 | 325 | 338 | 351 
12 364 | 377 | 390 | 403 | 416 | 429 | 442 | 455 | 468 | 481 
13 494 | 508 | 528 | 534 | 547 | 564 | 574 | 588 | 601 | 614 
14 628 | 641 | 655 | 669 | 682 | 696 | 710 | 723 | 737 | 751 
15 765 | 779 | 793 | 806 | 820 | 834 | 848 | 862 ! 877 | 8o1 
16 905 | 919 | 933 | 947 | 962 | 976 | 990 |*o05 |*org *034 
17 | 0.2048 | 083 | 077 | 092 | 107 | 121 | 136 | 151 | 166 | 180 
18 195 | 210 | 225 | 240 | 255 | 270 | 285 | 300 | 315 | 331 
19 346 | 361 | 376 | 392 | 407 | 422 | 438 | 453 | 469 | 484 





1 Obach—Ostwald, Z. IT. 566. 






































APPENDIX. 145 
TABLE FOR THE VALUE OF ———. (Continued.) 
1000 —@a 
° I 2 3 4 5 6 7 8 9 

20 | 0.2500°| 516 | 531 | 547 | 563 | 579 | 595 | 610 | 626 | 642 
21 658 | 674 | 690 | 707 | 723 | 739 | 755 | 771 | 788 | 804 
22° 821 | 837 | 854 | 870 | 887 | 903 | 920 | 937 | 953 | 970 
23 987 |*004 |*o21 |*038 |*055 *072 |*08gq |*106 |*123 |*141 
24 | 0.3158 | 175 | 193 | 210 | 228 | 245 | 263 | 280 | 298 | 316 
25 333 | 351 | 369 | 387 | 405 | 423 | 441 | 459 | 477 | 495 
26 514 | 532 | 550 | 569 | 587 | 605 | 624 | 643 | 661 | 680 
27 699 | 717 | 736 | 755 | 774 | 793 | 812 | 831 | 850 | 870 
28 88g | 908 | 928 | 947 | 967 | 986 |*006 ;*025 |*045 |*065 
29 | 0.4085 | 104 | 124 | 144 | 104 | 184 | 205 | 225 | 245 | 265 
30 286 | 306 | 327 | 347 | 365 | 389 | 409 | 430 | 451 | 472 
31 493 | 514 | 535 | 556 | 577 | 599 | 620 | 641 | 663 | 684 
32 706 | 728 | 749 | 771 | 793 | 815 | 837 | 859 | 881 | 903 
33 925 | 948 | 970 | 993 |*o15 |*038 |*o60 |*083 |*106 |*129 
34 | 0.5152 | 175 | 198 | 221 | 244 | 267 | 291 | 314 | 337 | 361 
35 385 | 408 | 432 | 456 | 480 | 504 | 528 | 552 | 576 | 6or 
36 625 | 650 | 674 | 699 | 721 | 748 | 773 | 798 | 813 | 848 
37 873 | 898 | 924 | 949 | 974 |*o00 |*026 |*o051 |*077 |*163 
38 | 0.6129 | 155 | 181 | 208 | 234 | 260 | 287 | 313 | 340 | 367 
39 393 | 420 | 447 | 475 | 502 | 529 | 556 | 584 | 611 | 639 
40 667 | 695 | 722 | 750 | 779 | 807 | 835 | 863 | 892 | gar 
4I 949 | 978 |*007 |*036 |*065 |*ogq |*123 |*153 |*182 |*212 
42 | 0.7241 | 271 | 30% | 331 | 361 | 391 | 422 | 452 | 483 | 513 
43 544 | 575 | 606 | 637 | 668 | 699 | 731 | 762 |*794 | 825 
44 857 | 889 | 921 | 953 | 986 |*or8 O51 *083 | 116 |*149 
45 | 0.8182 | 215 | 248 | 282 | 315 | 349 | 382 | 416 | 450 | 484 
46 519 | 553 | 587 | 622 | 657 | 692 | 727 | 762 | 797 | 832 
47 868 | 904 | 939 | 975 *orr |*048 |*o84 |*121 |*157 |*194 
48 | 0.9231 | 268 | 305 | 342 | 380 | 418 | 455 | 493 | 531 | 570 
49 608 | 646 | 685 | 724 | 763 | 802 | 841 | 881 | g20 | 960 
50 | I.000 004 | 008 | O12 | 016 | 020 | 024 | 028 | 033 | 037 
51 O41 045 | 049 | 053 | 058 | 062 | 066 | 070 | 075 | 079 
52 083 088 | O92 | 096 | Ior | 105 | 110 | 114 | 11g | 123 
53 128 132 | 137 | 143] 346.) 75r [155 }-160 | 265 | 3169 
54 174 179 | 183 | 188 | 193 | 198 | 203 | 208 | 212 | 217 

! pat os 
55 222 227 ; 232 | 237 | 242 | 247 | 252 | 257 | 262 |-268 
56 273 | 278 | 283 | 288 294 | 299 | 304 | 309 | 315 | 320 
57 326 | 331 | 336 | 342 | 347 | 353 | 358 | 364 | 370 | 375 
58 381 | 387 | 392 | 398 | 404 | 410 | 415 | 42I | 427 | 433 
59 439 | 445 | 451 | 457 | 463 | 469 | 475 | 484 | 488 | 494 
































146 


APPENDIX. 


fusee 





BRAR} 
OF THE 
UNIVERSITY 


OF 










































































TABLE FOR THE VALUE OF tine 

° I 2 3 4 5 6 7 8 9 
60 | 1.500 | 506 | 513 | 519 | 525 | 532 | 538 | 545 | 551 | 556 
61 564 | 571 | 577 | 584 | 591 | 597 | 604 | O11 | 618 | 625 
62 632 639 | 646 | 653 | 660 | 667 | 674 | 681 | 688 | 695 
63 703 | 710 | 717 | 725 | 732 | 740 | 747 | 755 | 762 | 770 
64 778 786 | 793 | 801 | 809 | 817 | 825 | 833 | 841 | 849 
65 857 | 865 | 874 | 882 | 890 | 899 | 907 ) 915 | 924 | 933 
66 941 | 950 | 959 | 967 | 976 | 985 | 994 |*003 |*or2 |*o21 
67 | 2.030 | 040 } 049 | 058 | 067 | 077 | 086 | 096 | 106 | 115 
68 125 135 | 145 | 155 | 165 | 175 | 185 | 195 | 205 | 215 
69 226 236 | 247 | 257 | 268 | 279 | 289 | 300 | 311 | 322 
70 333 | 344 | 356 | 367 | 378 | 390 | gor | 413 | 425 | 436 
71 448 | 460 | 472 | 484 | 497 | 509 | 521 | 534 | 546 | 559 
72 571 584 | 597 | 610 | 623 | 636 | 650 | 663 | 676 | 690 
73 704 | 717 | 731 | 745 | 759 | 774 | 788 | 802 | 817 | 831 
74 846 | 861 | 876 | 891 | 906 | 922 | 937 | 953 | 968 | 984 
75 | 3.000 j 016 | 032 | O49 | 065 | 082 | 098 | II5 | 132 | 149 
76 167 184 | 202 | 219 | 237 | 255 | 274 | 292 | 310 | 329 
77 348 | 367 | 386 | 405 | 425 | 444 | 464 | 484 | 505 | 525 
78 545 | 566 | 587 | 608 | 630 | 651 | 673 | 695 | 717 | 739 
79 762 | 785 | 808 | 831 | 854 | 878 | go2 | 926 | 950 | 975 
80 | 4.000 | 025 | o51 | 076 | 102 | 128 | 155 | 181 | 208 | 236 
81 263 | 291 | 319 | 348 | 376 | 405 | 435 | 465 | 495 | 525 
82 556 587 | 618 | 650 | 682 | 714 | 747 | 780 | 814 | 848 
83 882 | 917 | 952 | 988 |*o24 |*o6r |*og8 |*135 |*173 |*2I1 
84 | 5-250 | 289 | 329 | 369 | 410 | 452 | 494 | 536 | 579 | 623 
85 667 | 711 | 757 | 803 | 849 | 897 | 944 | 993 |*042 |*og2 
86 | 6.143 | 194 | 246 | 299 | 353 | 407 | 463 | 519 | 576 | 654 
87 692 | 752 | 813 | 874 | 937 |*o0o |*065 |*130 |*197 |*264 
88~| 7-333 | 403 | 475 | 547 | 621 | 696 | 772 | 850 | 929 |*o0g 
89 | 8.091 | 174 | 259 | 346 | 434 | 524 | 615 | 769 | 804 | gor 
go g.000 | IOI ! 204 | 309 | 417 | 526 | 638 | 753 | 870 | 989 
QI | I0.II |10.33|/10. 36/10. 49/10.63 10.77,10.g0, I1.05/11.20 11.35 
g2 | 11.50 |11.66)11.82)11.99/12. 1612.33 12.51/12. 70/12.89 13 08 
93 | 13.29 |13.49'13.71/13.93/14.15)14. 38) 14.63 14.87|15.13 15.39 
94 | 15.67 /|15.95|16.24|16.54|16.8617.1817.52:17.87|18 23,18 61 
95 | 19.00 |19.41/19.83|20. 28/20. 74 21.22 21.73 22.26 22. 81 23.39 
g6 |. 24.00 |24.64/25.32/26.03/26. 78 27. 57/28. . 41/29. 30/30.25 31.26 
97 | 32.33 |33-48)34.71|36.04|37-46 39.00 40. 67/42. 48|44-45 46.62 
98 | 49.00 [51.6 [54.6 |57.8 |61.5 (65.7 |70.4 |75.9 |82.3 89.9 
99 | 99.0 | 110 | 124 | 142 | 166 | 199 | 249 | 332 | 499 | 999 





INDEX. 


Note.—The names of authors are printed in italics. 


A 
PAGE 
INCOTIC: ACIG Bhs idee csi ies aie ba eee oe Srevaseve areca oa eh es 4 
PLACA tee saat nia Miniais Wea hla a Greco emi ie ea sues siete 6,10 
BUY ATIC! rns ysass sate sre aes ais eee ae eceaaes 6, 8, 10, 112 
Acetylation, methods: oF. .5-2.0005<.24 200 6, 95, 97, 98, 106, 112 
Reety Drone ti ees aces ood erred erat a say wie caive ties 6,8 
CHVOTIOR Ce ee ides + ncaa ns ea ae ete ahh 2) hae anes ais 6,9 
GETIVAUIVES: ISOIAUOMN econ core eee ee Sores 10 
PrepavaviGnre c.f ee ee ys el a oes 6 
eroups, determiuinavion. 46 26 y ek Wee cee eee twice II 
additive: method i205 2.022405 3 18 
distillation method.......... 19 
hydrolytic method.......... II 
potassium acetate method.... 18 
Acids, determination by indirect methods.............. 48, 58 
electrolytic: condguctivity.<. ice eee 48, 53 
CEREPINCALIONS Jaco is coeadle ts BSS ea eae ats ee AOE 
Sea ise ee a pine Le el Cee ee nee 48,409 
EECA CLOW re ee ie ee ee ee ee ee ie raat 48, 50 
ICVIAtiOW ss Jes eye rds Waive eee oh cere nye eaves 4, 30 
PIO ERD: Pic ote kL Oy cease ea ey ie eR ey 8,12 
BIG OSAMOESS Nel a is ne aha tate Bena are ate nal Seen ete tet 80 


Aliphatic amine groups, determination: 5 .2.3......2.424% 02 5 


diazo compounds.......... eae gr arapae 1°, 


titration with iodine........... 120 

Aticalowds (itrationie 22262 cite ee shes wee chars 98 
IE VIGGON ie eo nce eo ee wate ee ee eee ood, TOS 
OF RYGrox yl PrOuUpsiain civics ose eine ae 31 


148 INDEX. 


PAGE 
Alkyl groups determination, 002i se visas. ee ccc asn dl 4 et eq: 


AON Ady seca s ees ea Sh as SOE 


Ee CEP EEE Cee Ee er or ee bere ee 53 
FN ES So oa so es eres ere ees fea ee Ne dS eG eS ee ae 120 
Prnines, acetytation: 6 5. 55 os ha ce soe Freleng ase 90, 91, 106 

Aleylation 56s s 6s eres cea ees ea ee 108 

salts. pea eee Se OVERS Ge or. 105 

 Asoinedimeth ylaniline derivatives. aos a aSoue rer ene 68, 92 

Amino group, aliphatic ................ Soaert hon tae 95 

RVOMALME ae ke er oe vas omens 97 

CIOLETININIAVION © 05) Sine ag oe ws 5 aa 8 tee eae 95, 110 

vAsminneumrwine ncarbonate. os 6 2s ge cde coe ees gt 
CTI VACI VOSS. osc 2k ke os a os PE 68,90 . 

PIOTALE GCTIVATIVES |. ooo)s sss ga phe eS eds 88, 92 

GAN Sees Whe ha re eee Le as go 

Ammonia, Byars. Woe a see eae sy1l, 34 

AWG es a BENS CES ee a es es 5,69 

PUM AS eo ee cs LARTEEE gi AE wie he ROS Ws © oF ee 104 

PERS N EE Fos as vice ee ee oes We eae al ee Bae <1 52 

POMEOUS VOPOUTe TONSOD oe ooo '6 a0 Oe oe cos 8 ee ee 144 

yarniserong: foe eo) Oe ha Le aes Ging Ba ek lw 8 


Aromatic amino compounds, acetylation 
diazo derivatives. ...........97,99 

Salta OF ks Seka cee OTS Oe 

groups, determination. 5.0.56 6050. bs 6 OS OF 


Giaz0 COMPOURES | 5 a Ts i Ge SS 120,123 
PRONASI EP. FO SST eas Oe Ee Sa ee eos 135 
TOWNE? PAs SOs i as Oe Leelee Male Caw y Ree eon a 51 
A WwerS FAS NS UE ek eee eee ee 33, 81, 110 
Azo dyes... : i icecus poet eo: 
Azoimide pabthion fie determination of amino group. ody 98, 102 

B 
Beyer Ale Cee a eee A 84, 87, 90, 106, 136 
BaRrewtn, Mog Oe so as ee a ee ee 33 
Bamberger Fes ries as Fics TO ees 
BA cies AG Cee ee GL A ee 6,41, 44 


Barium hydroxide, hydrolysis bYy.:. .<..s.5 469 i-s a Go ee 
salts in carbonyl determination..................68, 93 
BOG io iy ae FRR EE Fe 14, 24 


INDEX. 149 


PAGE 
POPU ae oes 25 eG SaaS aa nal 8 So alae e evauk cas ew bere Rie arwls 54 
Basicity of acids, determination by ammonia........ 48, 58, 59 
CarpOnatesi sve: 48, 58 

electrolytic conductiv- 
BUY Si ssaee cote eek ate rod 48, 53 
etherification: <.. 0.6.5. 48, 51 


MOOMIG) 051d 425.9254 05 501 04 


SHUG ees ais via a oes 48, 49 

SUTAUONE ee 48, 50 

go 77771 Wy ae na het ewer mei eg Mp aN eR cat ee ay tan RRR tae hed Roky We 71,03 
DAUMARW OREO Ses eet ee ee arte A322 24, 22..64.605 E42 
FSCCRINONIO Ss rc tone sel ard ieee SAVE Hise Re ER ae mae 16,-30547 
TERCUARE SS oor gird ee Nee ee de 5,12, 40, 41, 44, 74,.75, 136 
DBenzene AnG water: TENSION: jc.0 so 7s 10, faa i aie ee 
sulphonic: chlorides jis. toe ee ache ee Sane eres 107 

Benzoic acid.. Patel ference liek te Syne da stietscc ire Be PON SN Ai pe 4 
acids, eaneited: Bd O EA bine ee Te Let a yaad cin a 4 

TSE VERELCC Foire sus a orccrtunt ides hv tarae Nie ook a eaten ZT i256 

Benzoyl chloride: oo aie eee aa wie Oe Rep eee ak 
derivatives. analysis i sc Cx seta ee sae 28 
Preparation. ont ck Mel at doe oe cad 

Benzyl er vaAtvese ce eerie ie cae A ace ES 443 
phenylhydrazine, in carbonyl determination....... 74 

PIOVU CLOUD ors aaa he ryer s dathgin masta Skea ry Cad tt sigs og ee — 
PSI BUREN De 8 Ouro g hs cna bern ae one HA ee ne 83 
dU E61 AGS Ch Bae pear acheter eC RT On te RO ence eer a er EE 96 
UCTS 25 etude Ne OU cee Roa ton RENIN Mh cence eee 119 
TS OMDCARL Es reo ee Ne ed te CA TEE ee Cc eee 110, ‘III 
BOWLER IW Dee ae ae eet Ee ai ele metere Say oe ear 53 
PP QUGHOGE. VSO Ce Creat tii Se eee ae 6 
ESPEN OT Te ae RE OE ies eR aetes RTE 88 
p-Brombenzenesulphonic chloride. } 4%. s.0.3 65s. 5542 s<- 107 
P-BLOMpENZOIC ANNYV UNOS M6 Fc cee rie Caan ateae 25 260;27 


O-Brombenzoyl CHIONUG diese nue ee ee ae en ceo aed 
p-Brombenzoyl chlorides 3.04 sence abine aa homeware eel, 20729 


p-Bromiphenyihydrazine oi neo ce ute teen eee 72 
TEVUAW TS AG ee nk Nene ae ae te oe aa ge NG pean 74 
BUCHRO oe a ee he Benn eh cet ee ne ne eas rite: Sete es 19 
PSL OUE EE Re eg Stas ecw korg oT EO ee a 106 


150 INDEX. 


C 

PAGE 

CRORE oS eo eosin wn GNA os FANS Le doe Rae ie 58 

CORR ALS ec Ao 0b 5 ed UR WAS E OEE ES ate 92 

COE Re BU, We a Oe wee As OER aeons sui eteeene aes 109 

CWIOE TE 5 Fos sas ce DAee RD Gan Rea eaeos Ee er er 84 

Calcium Bavbonte. hydrolysis De es at ewe II, 14 

CET PAINALOBS SS sk oe oa ASR RN eae Oe Sek Pa es 4 

PTEPATANON 2c ANAGs dahon Oe eg eee as 33, 34 

Carbanyt chloride, preparation: . 2.60 v0. bcs sss bc ee ees 33 

Carnot Ceternuna tion. fa ag sa oo he eS 68 

by phenylhydrazine ............ 68 

substituted phenylhydrazines.. 68 

SHCISRES SDELNOG Ss oboe ek cea 68,74 

Carbenyi deternnnaticn ye a ke eS ce whew Sib. Boos 38, 48 

by electrolytic conductivity........48, 53 

etherification= (350.66 75055. 48, 51 

Melt Amary ete do ow ae 48, 49 

Sit PATON: 0005 3 LOS OY ee eek OE BO 

USER ag 5 Oe ae ee 48 

by ammonia. ....... 48, 58, 59 

carbonates. ios 48, 58 

hydrogen sulphide 48, 58, 60 

TORINO ESS oes 48, 58, 64 

COTTE oe cee De gl eae ae 8 Re CAVE oa res Se 53 

Caspar We A eho iS Ea Pee 36 

COGMSSE FB ace ee Ra LS ee hc ie eS ae eRe 129 

CC NEMAE? ok OE oe Oe ab ODE Ee ET OR a OS 104 

Chalk: Dydroly sie: WY i905 <io5 kad bord Ba ee as Ca eee ae 
CREDO ox 5 CSS Ed Oa ES ead 

Charante; 9) Mo wate Gece Eh Dees hd oa ae eed oe 47 

Chioracetyl chloride 2527 2 i ts Bape oak a ee 6,10 

4~2-4-Chlofdinitrobenzene 24206 3455 ead eo oe eee es 37 

p-Chiorphenylhydrazine (33.03.0046 feck ca dx ci pee ans aed 74 

CAGINWIAR Fo Se ei hk hy Oe 16, 18, 119 

CLAASOH LEAH ee ed Reed Lhe CER ee OO as 7, 28,27 

AUS 5 928s ODE Rae oo REARS ORES 83, II0 

Glauser Rods os Spee bak eR CEO a ee 132 

Cowes, Go. Ai iets ee CRA ae ee es 94 

Cohen, Bo heb ie 1 eee s eA 54,55 


INDEX. 151 


PAGE 
Copper, reagent for amino group so 0.06 66 665 cies cic. b eens 104 
CURSING < cote oss eisicedn Cue ace Peale Pb Ue iar waianene. ee serosa eats 83 
Cuprous chloride, reagent for amino group............ 103;.123 
CORPUS Po ee a eee es 84, 93, 103, 120, 121, 122, 127 
D 
DDANRCRWOMN rg 2 acidic SROAT ree fe DEE Oat oreo elie 12,22 
DV GUICS Seg ie rsh, elev due Pessina (ha PANO Rae IN 83 
DIOS A et eA ec aa eR ak AR adr le he na Sor ad oed 25 
CA GH eRe ee ante tied Pa ee en ee ee ea 103 
DBS Fg Pah ESCO ee Rie Cert per era Po Ep Un nacene aie coe aie ci Gary ges IIO 
DIE DE LOG PE i Lene eta Ces Ree eR ee eRe ogc oar 99, I12 
Dele pines nein: oe ean Beene dpe Cie ee eto etre eed recy Bak ene 97 
DI EUIN LOTS IN feces tare aes Nek wh eRe ee ONE REE ad cd Sey a PG 
TIE DIUAIE Je Oa nye ee Utes A ae Leto 9 
Diazo compounds aliphatic... 32 sinc cs tie eee Paso 120 
ATOMALICS Poh oso sa eincis: 2 eset 99, 120, 123 
Preparablonsa.. cote ee Ae es 99, IOI 
SPOUT), “CLEEMIBAMONN 6 eet ey Rees pene 120 et seq: 
methane, reagent for Hydroxyl) (ose oo ot 32 
method for determination of nitro group........... 132 
PiaZOniun WEnVALVESA coir > cs ee ei eee te oe $20; 423 
Dibromphetiy thydrazine << v.05 e4 yates Lhd hae k y ces 74 
m-DuodopnenylnydraZzine <4 5... the oe ae Be eg te 74 
Dimethylsulphate, reagent for hydroxyl............... 32, 108 
Diphenylcarbamyl chloride, preparation................. 34 
Pipleny Ny draciwie cidohe oe oe eee eee Sen NY oi one 74 
PI OOTP ET ME ie ORS Roars we al tod has ait 2I 
E 
TEOOTE irs CoS ee GBA ie bie UMN AOU rtd eal Co tad cetre ec eed Yi; 
BORO ate sn oe en ON ae LAr Cent eee a ee STU Aan on ay 
EE GRCNSLOUR AUR ey ra oe ie a Cee er Oe ae eos ke 74 
ESCRNOT OR in oleae Re Reg ye ed a gen a tah) Renee 2 49 
PONNGI TE soo 5a AD ae ors he Se ee ee ee 41 
PEFUICIO SS Ei eek pees iene eared fee primate ees aa 5 
DS a ibd Urata le gee OEP Canes i Bg taties eoh Cua Ret RSS ope 107 
PGRNOTH A ats ones eet Sn ee Gene Ge ee ee R225 Ge G3 


DOLD ENS tase aes ae ghia eign gid oe Rees escrow a Se 70 


152 INDEX. 


PAGE 
Electrolytic conductivity of sodium salts................ 53 
EO DRT AINE ES oS a Fic Ren MOSES OS Se ee Hl Nes SSE 70 
POP RS ee ens guia te ec eee he Ke 109, LIO 
TVIMAIEY 2 Feo Fin CS Pee EROS CE RL! 13, 19, 34, 100 
PERI ote oO DCE tea a Fe 19 
Esterhcation Of BCS so eles rcs ek en eee 48, 51 
Lthermeation of phenols 2 oo oe ei Se a 3 
Ethoxyl, and methoxyl, differentiation.. ............0..5 47 
Cevermination. 3 GAC ee ee Sa eee eR 38, 48 
Ethylimide and methylimide, differentiation. ............ 119 
GELCEMINAtION. <6 kos i cae oo eee eines 95,119 

F 
Pee Ping ern ao 5 Sess ay EK DOE TRE hd aA OKT ETE 48 
TCU ee iy Se Gia Ope FOE CE EER Sn belgie RHE EM 7,25 
POUR sais Be ee ek We a Be ee ers 8 he ER, OG 7 83 
Fettleerens Sees Cees Ee Pe bien cing Ap EA eee 104 
Penner ae Se RE So Ce ek Ce Sa dg ee eles 106 
Paste 8 oo ee ee §, 23, §2, 60,:76, 71, 73, 407, 108, 154 
PGI Na os 5 eNOS ee nt oan pa Be pao Na Seok cae ae 31 
TEPIMCHUINONE 5. RAL ES co ee acd Ha eh a Oe ae te 9 
PEGORIES i PSUS BOS 4 SES Pee GP es Wav he We waa 19 
POROUS BN Se ces Dia a ek LORS ORO EN BAK Seba eee 
DIONSE a ok os UR 6 SRE ER CT A ie ee 9 
FPO AUOET. Fo os Sako SSE Oe Se th WS Se 14 
TPC eo A PES oak ae ik ee 123 
PRPS Eo ee ed ala Fro aah ol ark ee Aue patentee 60, 64 
Pia ATS Sse oo re Pe ek ee BR RS 51 
POSE Fe ay cee ae Ua es ee ee 73 

G 
CRETE, Bee ho ob ok bb Raw ES CN EE a wa ea cea 70 
Garellt,.. 0, GE ee re aN ee ee Peg Oe 82 
CSOHOTNEANTE, Bo OS ES CS Be OL ARE AR AE, DEE S48 
Gattermann-Sandmeyer’s reaction ..........2.2.e00%+ 98, 103 
Ceorgesca M28 OE at Fa ee is a ee 28 
Grersenhewmers fo eo ei a ee a ee 52 
TWAT O. Boe oa oe a Ca ye Oe et ee 5 
NS SP AL 5 2 ek ats, ie EG NE eae ce oan ee eo 113 


Goldschmidt, Hise telece xorg Coe ek CE ee 37,123 


INDEX. 153 


PAGE 

GOMISCHINSOGE ss ped a ws bas cc Ov abe ces KTR, TO; 21, 24; 20,35,555) 59 
Gordin, H. M........ Se sce Cees Lusi gs Bee eleie's abun sata wial Oe 
Grace Fes eee See Siu cine ns Sage ae 
CT GHOUINDNOUI 5 one ew da VR ee eee elesian Siete oe ere cies 103 
GHC AG ig cae eles oR ase hoo Selec alet Paediatr tye 102 
ICBO fe aie eee Pe eNO ae eee Ar rire 6, 67 
VICI SS Eat Foc e Gk ot) eee ahuiid tds Bee ate atk ase Re RISC RD 102 
STO CER IIE hes aie tes oly GRE IE eat cag canayg A oy etaea mieed Micpawite ater 67 
GTOLOWSEV TL te i ea ns & ad ae Re AS ae es 106 
GEUSSHOT os ee. Ua ere ee eV ee tae 40 
GIMME ETT ok scdisin ae hodso 6 ian std cdlk- wader Eee a is oevere oie Eas 36 
(GUVOL ok Loe eno kent oes et IT oa meee ee 33 

H 

FE OGCI oa ee esas Bek oreo Ne de ee Die a as Viewer ieee 8 co, 63 
FLOUR GER re ie dies es acho ee Re OS nk oy ee 50 
PRES Boe ere ees a rcs Usd ae eh dae ee aaron eeccaty tails 33 
PLOVEZSCN ose ee ee Oe) Vk ete) Ga nate neal oe T10,.124 
PIOIDE PIC TOG Gc eo iis ery hee ne Sle athe ae ee Sone 99, 112 
FLOPS Gre orate ek ere PS este aie ee ore oo ee 84 
EP QUWURTHS 5 ao he sesh prs beta tts a ea ee 102 
TEOUIPNTICH OTR eS hg ete Gere ee ae fea hase ee ete 84 
PECORIMELINULYT ac Ase tek eee Sets ore £82120, 59,70 
TL EWIRQUES OI eS ea Sines Reon Ee ee 136 
PEEPS TCHS oo en a ened eta eee Nt cate CN EEONG BE Ls 8 au or 16, 92 
TI CTAIR shes ean tae 6550.71 37:20-37; 44,525.03; 124; £10; 116 
TeSSO5G cas che Oe es ee SS oes Wa Serre cused Prete s IOI 
TE CUSET SS as he en ce oie ae Gene ea ete One ee ik es eR 85 
fs i ] Sie oh Pg tee de SE hr Ne ee ee Pat eee eke ee AP ee ay ae Tit 
PT CER Ae Ohad eed kOe Ts EE eR DE 74 
TPA ERSOCE RE Ses epee rae eiaee LRN SG acts ome lee a ee 2731 
PIST SCHR oooa cee Oe ree Chee ee 100 
FLOP INANE NCH Score POR A ails, OM eae ee Oe Ce 83 
| A Ce RR? DY RIP Fees mn os et oyna gee Sees Fer 


PRO OWY Bs pie inns Ooats aera pene ieee See SS LOSS EOD 
TROUGREE De oe CNet ae Ue Ae are oe EA OE eS 


PEO eo oe BN ret Seats hed a ed pk cn alae eae Sed eee a 70 
TL OU CUTAITE ioe is ie Oe a 125 


FE OVMOLIIEG 8 eo ORE Oe Pee ne Ree tie Sates og ae oe pe ee 49, 81 


154 INDEX. 


PAGE 

FIG DANE Te no oh oc oe ue ed eee tk 136 
PEON Oa a a an Ee A ge ee eee 4,9 
FER ois. oop a er A Be SE REI NE EG 136 
PEW ree oR a ees Ck RG eee a a we Se ECAC SS 34 
FESO io eS Sate eee Le eee es eee 73 
Hydrazide group, determination... oi... 0.6 eee ets 120,125 
Pane DY F0GING. 0. 5s ies cece 125,127 
Hydrazides;, oxidation .. 0... J.5..... Pacem er gery he 125 
reagents for CAPDORYL ooo ons ea Ss 92,93 

Hydrazones, substituted, preparation. .................. ¥3 


Hydsiodic acid, fiydrotysis bys oo Se ae SF 


Hydrochloric acid, hydrolysis by. :...... 0.2.0. eee 11, 15,109 
PAM AURORE OE BOC eg digs Sa awd San woe 142 
Hydrolytic methods for determination of acetyl.......... II 
Hdroxyl, determination....... iad oo eae, Ges uaa 4M 
Hydroxylamine, reagent for copense Oe oe kW actuate oy Oe 
HYGMCHIOTICO’ Foye es eke ee as ov Des 3 Be 

I 
TORT EP 5.5 5s) BS chy he tote e DENS OK EEG ae bs eee 51 
TICE ACCU VIATIOS oo oF + os CAG RR RR a ees bak eh ons 112 
VION ae ere si See yy yaa eroticy Ca a eee oe bea 113 
ee es SOROS, Fela ori a suc aid eas Veen 113 
Imidogen, elimination as ammonia................+-+5. 113 
Tmido:protn, determination os oo se avs be cao ae e 95,112 
AEP OGUCHONR soit oa ae We ee! hp he aie bo ea ee I 
Iodine number. . peeien Gin: oe a ERO, eae 
Iododerivatives ok ain icetie dines commons: Be DET igs 8 Ts nae FE 
PAndophehylnyGragine 0555 3 no soe sg Ca ewe aes a 74 
Todoso group, determination) 05 ry sie vee wcssy bees 120, 134 
lodoxy groun, determinations) 0720. ek eee ee 120, 134 
TPE Si oe a aR Gy Ae eet ie ae a Ke 125, 129 
TSODULY TIC MOI oi 8 oe Ge aes a ee 4 
ONNVATGES SO Rei i es We ee ee 30 
Igobutyryl derivatives 65635556. ge PS ewe We wee bee kes 31 


FOERSON OF 6 Docc soos 04.5 0 tA VEN AGAR S BED PRESS eS ees 27 
JACODSON Pe ie aw ks 85 a ie Vee ea ene ae 33,92, 109, 112 


INDEX. 155 


PAGE 
CL) | tage Beran a eae RAPS et anny our ht ay ernie mre 24 
SPONODG, Is ei a Ree ree eae ne Gee oe KS ort ipirdate nis 21 
PORN EROS Cea sce ee ee APRA A eae re tis eshem eas 80 
PGSSOV: oa ros ee ale cio ee ies pale wate Ev aioe einer es 31 
J CAMETOMG Coot ce giiritis cress ya ewe ate ae ee Ng ae Te 83 
PEN Goa ire Ce ete Oe ee ee ec eA a Sele ees 59 
 PORSSOR ec eeG as 6 Ba seme pete 4 eres ene ee eee SRS ses 129 
ONES. IV CUGPMNGIT Fy rene oan g Sar a en oe des 109 
ER eae Re ES ative de Ma Eo Ses ea See aaa 
FUSE ASIA se atetig Wid, ce Ree ale Gt eR tH SIEHS eee he oe : 
K 
TS OSOVER AE os aos at Spee ares GE Vigo Cer Oa eas 52 
TCCHTINGHR erent ek odo Pe ea es MR 82, 83, 106 
TS OUD WV Sie cre etree gare eines a ce Me iaorig: WL cree teen eat go 
KetORs MGS See eo a cay Soh aes cage ishers Rusia ace ie eon ee eee 81 
FAN MICUTE TS CP a aati ig oi OER FON SUN 102 
ES TAIN ONE sare eter hoa Se ght are os en ge etapa a Sena ae Soe ee 139 
TOIODUROWSE 28 ol Ae RAS otes MUR L ee elena ee 10,13 
TER OVATE Ld aa on ree TERME ete hatin SAE hake rs Same iss Te ee eGR 53 
TE MOCDEN ABO! oe ens Maree ee eis Sah Cle dd Bed ee 123 
1 iG 76 area a eee a ara eae Neer eee er ne per ani eer, may Aenea 6 
TNOTE Tis oen. ces $ Cie 
| Pare ee Be lara tee ehcbar tee gre eee ote acer Mase a eee eae 30, 36, 51 
TDCREES WES ince cou eres Mees Wine PaO RT 6 eae he ee 
IORIPAUSEU ee ois or erat aa oot oer pin tss Cine Ines 55.57 
UC ORI ho ee eT eos Pinna aoe miata aid Mite eG) ete aie eee 6 
TOT ONN WY o ok Noe oe Nake Bh eM ae ea AOE EO Oke Ee 96 
ICOSEAR CORE ere es de Lats Ieee ak IE SO eas se ee 32, 82 
ISA OMBS Foot eos, Wed WEE See ees, ial bin rata ORONO er Ms ee ae 73 
TFB ELS gp ied atrrecas este take Sites oes ee ee ee eee Ts | 
TRIES A oe i ere eas Miu aneca geet Staci er ae ee ee ee 136 
PMR os Ore eae eee ae Tie pes ER es ON Ree 64 
L 
EO CORB 2 oe SG sta ee ee Oe HEB CRE he 9 
EGON MEE Sa ccc oes pes Sioa icles es alae laca eee are ateieis IIo 
EAMESSOUE sods oocyte i Tee eee 6 


156 INDEX. 


PAGE 
ERESOTAS ON ooh. oe 58 CNN RRS Se RT es 49 
PORNBB Eo. Be EEN ee OOS ee RENE A 84 
LOWRORUGN Fos 0d Soe 9 se ob So REE Fae SS 136, 137, 139 
TMI eo as ohne PER CS EN oh Ee gee et 12,14, 50 
TMOIOIIE  S SN Ee ee ee aa oS ood Lay Op Sen ee OS Sa 
PUTO EE oss os Pe kes Soe iets ees ie ts 
SIM oie ose Sas FS eo EGA OE ES hee ee 4,29, 23 
MOE Gon hes Sat oe Ca eee ee ee ae wes eae eG 110 
M 
Meomens. hyGroiysis by... oo. ia cic sec esi Success II, 14 
Magnesium alkyl compounds......... SELES 0:09 '¢ ole eis 37 
DEAE Ss es ney eB Gilk eae re ae es Uh 23, 43 
PRE CBPRNIE os as ss putas heh Oke Ap Oo + ha ee me ke 107 
NI 6 Sal ie He so LS Seca a aes ERO Re eo 9 
Re CE ee ales ERG RUSS Cees bib S hae rad 60 
PATE ic os eis Qe ee ER eh LR Se 124 
AICTE ss SS ES Se eau peo es 37 
DE CU he Gon Bs a 6 EERE TS OE og dO eas 102 
DEOMI soe Kd bo ko BRERA SG on 8 oO wee Be aes IIo 
Menschutkin 98 
PEIN oo sk ode Nye! EO ie Fe Reto eae le Ghd WS SHU EN A eR 123 


Methoxyl, determination (Ziesel’s MGtROW) ss 5 cn bess es vga ae 
modified ...40, 45, 46 


in presence of methylimide...... 117 

differentiation from ethoxyl.... 2.00. cies 47 
Methyleteé, determination... Pies ny os ew a ee a 94 
Methylimide and ethylimide, differentiation.............. 119 
determination ......0.5.5.5 95,114 
determination in presence of methoxyl...... 117 
Methylphenylhydrazine, reagent for carbonyl............ 74 
PEON FRE ae vec RY US & TNS IEE Re ae es 31 
Meyrnvure (Fo VU, class ca tee ee a eae PP ae Bat 81 
PAGES on ee CR Cons Mb bees ep eee bawnes (cwew ee ees 49 
Be BERS EE I GL 2  NG Ca  e ee 127 

BD sii, Cas 5 ee, Ss 20, 29, 44, 64, 114, 118, 119, 126 

Wee acces ieacsls “ae .20, 29, 70 

V 945 25533; ae 90, oe be fe 92, Soe: I10, III, 112,135 
Michael, H. A.. te aie Sw een eee .9, 20, 72, 84 
WA ICROCNIS 30 5 R AN C8 8 oe ds bie kA EE 72 
Michel Ooo ee o a 8 a FL ae 103 


INDEX. 157 


PAGE 
Monopyrocatecholcarbonic WYOTAROR) 5555 sic oe ceed 93 
WA MMO ie ge OE i Fe ROE Grete SER ee OES IIo 


DE GUCHMN OVER 2 Aico aon ves ee SOS Hoe OR eae CES 


N 
B-Naphthalenestsiphome-chioride: <. v255.4 205s eee et 108 
B-N abs is hag Sabres reagent for ee aren 74 
Ne], J: U2 ote tly ae ee ae ee 70,9 1,93, 102 
IN EUDCE OC eek Rens ee De ete iehine aONin eel a yes cae ne fee 
NGHAOH ET AT Peo eee se SIL SE es 2S ela ae es Oe 14 
IN GUTOUD, FUN eet in cities StnE saey ae tie cart ore eg ee 74 
DT ae) ae Cie Dear ae caer eee Ne Se ame N RNY ame alae or I1l 
IN CUNMGNIE WY roo oo IO ed ce en Se GO eS eer a 89 
IN GCLERE red A ne cae Ae Sasi eG ea aa teeme ra ak ats way eile Aas 82 
Nitrile croup, determination | s2ic sxe os eked eats 95,108 
INILISIOS DV OLOLUSIS Ch ets ch oan 4 sh ccna mea eee hes 109 
m-Nitrobenzenesulphonic chloride ................220085 107 
WNiiropenzZhydrazidesig cis o16 266% Bod Gah os eee ee ee g2 
m-Nitrobenzoyl chloride... Ae oe a0 Weegee 
Nitrogen, determination in ee Giaee beens {2 20,;52% 
INitrO. Proup GeterininaVion sak ie cor a ow eee ee 120, 129 


Dy Giazo snethodas esses gs ee 
* AMP AON acsend ce eG ogee eV SO 
§-Nitrophenylhydrazines 25 6s 2 este p teed oh ee bees 73 
NitTOSODENZ NY Grazidescs. i250 56 5G err bw oe res one eS 
Nitrosa-group, determination: 15.54 ..5005414:55 ected Oma 


Nitrous: acid; reagent for amino. group .2..5 30.34.40 95 
IN OMEN 28 Cre eas ce optate ias sea asl Und Pes ae arena ota ora Fa Sena aia 103 
O 
Obach.. kee srateteialacmee 5 s0eoe kee 
Enanthaldehyde, ment ee amino 9 group dn iecuapiraace spaers 95,97 
Tend ONT sae 5 Se Bae es a edt he ed eer, Leola 74 
OManic ACde. 6 sae sera etn phe av een ees Bae Geena SS 30 
OsAarOnesan 2 my ae gee Re ee a TOA ra ens see 71 
OST VY a Ae ig eu cea ra tore ee a ta ere 53,55; 144 
DEO eccnn eats ats Che ais NS Mo WAL EGE SORIA a Wiig RAE DOO 27 
UCTION ER he re AN AE Doar rl ha nth nee a 69, 72 

PS Siig oe Cian Ss aS ae Sey ee Greet Aaraist casas ne Cue ee 74 


158 INDEX. 


P 

PAGE 
PF GUOTUI Ve eee pe EEE eS i ONE SS 22 
PUES SUES OF tos bg abe ah en FE es Sees 70 
PEE SOM ee se Sie ae. ER ee a Rs Be 58 
PORCINE PR oe ek ue Oe ee 107 
PECRIMOI OE ie to EE Re ee 92, 32, 70; 323, 135 
CURA es rw be Ke OOS CE OO ew RGN bead 32 
POS Cas ORF eee RS Pog WEL hen ears EES es 49 
Peroxide’ group, determination .......-. 005 66.0 cee eee 120, 135 
WPT 5 CSc one 55. Gis oS CORTE a REE ARETE a ae 1255227 
PO iis he ob ate nn Hale EE hwy OE EA Ewe ieee 80 
PHENO GSbeRficatione:. ie Se ee be ae vaeery ales 33 

MPRA Ng Fs oop arg Se Pa ig =h be THES oa baths ols Fes, GRE 4- 
PREMVACELYE CDIOTICR. oo iii es ke ees ee res Tee RS 30, 31 
PRCSY CAPRI Res is oc Ek ee tS eee Sa ewe 4, 35 
Phenylcarbamic acid derivatives, preparation........... 4, 35 
Phenylhydrazine, reagent for carbonyl................. eo BS 
E GUDISETAEEOG Tho os sian oa cree re es 74 
Phenylhydrazones, preparation... 2.0... 0.0... cece ee cece 68 
substituted, preparation.......... 68, 72,73 

Phenylisocyanate; action on hydroxyl .................. 35 - 
DUCTOPAVION 085. ck ce oe ees Ca oe ek eee 
PHERViISUIPHONMIC AGIOS Ga ee ee ee aie SSR 4 
CUIOVIDE, (65 de caste diay eva agers Cok SO ORs Bly OF 
PUOSDROPIC. GBI: id, cata uebc enn ERs SAD eS ee eee ee 
AETV RLINOS Fo Bos Oe oe ie hh age 31 
ENGSPHOLAS ORVCHIGCIE F555 eae ts ee ek OS ee aS 7 
trichloride, 266 ola hawk bee one wae es Cee 7 
Pickara WR: IA a es Ges one is pees ORS wie APPIN RPE PDE 
FERRO oJ Sia Si bicce Bs nd PATO As BEE Tao en Reine» ook 106 
POVACT OME oS. Pork a SEE DE a CO EE IE 44 
Potassium hydroxide, hydrolysis by............... II, 12,109 
hydroxylamine sulphonate. ................. 80, 82 
PreOrane 25 O eR PUR as BE ed BLOAT Ee Ca ee 47 
PYOPIOMC AIG Hoe PSs Was cake eRe EE a oe 4 
anhydride 1550-3525 HOES sy Pe SN vo cite 30 
Propiony! derivativess 2350 iace cca eed Oi ea eee 31 
Prd homme) Deak 0 kw COR a oe 108 
PSCHOVE BR oe REE EEN Oe a EE 18 
Pian, Go fo Se ee EE 28,44 


INDEX. 159 


R 
PAGE 
DCU SES BOWS FeV eo aces rd re RD Pinkie Wey ie wera tore gostei tare: 110 
PROSCIEG ce ocr AE te Seed cate tere otaere aaa okey nate he 82 
TOCOUONE rs cin secs erigts tesiiits ee pier co iatern oem res ae P23 
TREUCEOUIID POD er pr Oe es ans eS Pea Oe ice MERE Ge 99, I12 
TCV CT AAs ce Oe he aes et eee cree rare a eas 58 
TECRATOS 1 WVU eA ele RL Oe ee SI aa Sena ee ads epee as oe eivic 51 
PRELCRL OS Fo ne Re AG Ree ee a OE EA calls 102 
De) Clie OE | ee eet, ete aR oalh or ge ro ny aera CPC Yee Meat rhe Eee 27 
WROTNENT ESSN OSS Ge te bs sig es ee ee ee ae en eos 74 
TOUTS Oso oG re One seater as ia pees cence tense Segoe eee 74 

S 
SICH SSO se fete conta So arte gra caren Bete ave Wai pe pees a oe alo nn eae Beet 96 
ales Or ACIOS -ANALVSISS Sirs corse eek novae 3 ies eel is 49 
DASES oy ec ohn a tar gee ceo stare oenta mae 98},105;, 113 
SQUAMCVER: rie cette. en en Co SE Ee ee 103 
sGattermann's Teaction:: ..6.decscud nea be peso, 103 
aS s (01 LRM teal a ABD Geen Neer Oeh ie OPT arnt aa Ee Se 5 
SOME Te ctr: cise ec stee e a ee Eat eae en ee UA Ane 70 
SCTE eas ails here a ea a ee ke ea 19 
SChO Nd er A Bosh wie 88, 89 
SS CRCHEN LS IR GD, A Niels eo hac eters ea eR In ore st ero ATE OPER 51 
CMAP ATED Cee tig whe sie di ihe eS hgh ea eee Pe le 28 
SIGHT Th PEL on cai an em talises Pare a eltns Gee ie wc eae 6, 14,18, 97 
SGI OMEGA ae tc. . 8 gre Eogh Wi tcues ce bain OS Cae 26, 27 
SOMPMEGE CG Pe oS EO crater Snes ate Aiea done No ele See OE a2 
SE MIICUCD ETE eNO ee nee he Pon Mine aa Cee ee anes 49 
SCHINOCIET cae steht feed oN ae ES ae ete oe eee Ate Lg 16 
SCHOUS: NU Recs ei ere hcd oh Fs wie a ah Ole whe a ea el ee ae 74 
SCHOD] Sacer etch © ep etka ca Suse Ce Sw Bec eS egg 26 
SEROUEN cc Sons occ ace adin sae eee ce ce OAL OO, ea (ae 
CHP EDEN ene ot CS chee oc egal seewles Fe ca Inari ere eh ane oes 24 
SCHMH ES Sicea Seats karat Sie eke ares ee ace es a 
POGUE Es is hy a git Lect meee na fees ews dae ad pe 19 
SORUMIC. an Dae alae et etnies eed 4 whe we EO ee ee 23,132 
SCWUIZCNDET COR en Shae ch ack aS Sara's Oa aes 2 8d OE wee Ie 16 


SCO SWICIS TA I ec pris ca vein cate wae rk oO ee von era eae ee 49 


160 INDEX. 


PAGE 

Seelig.. ates ib RASC Sen ky ey OF 
Becutesphaging hudsoohioride. pieparation er eevee oa as 86 
reagent fot carbOnyl 6 oes a 68 

salts, preperation: sees oON oak oe 84 

sulphate preparation: fo Oe eis a 87 
Semicarbazones, preparation... ...... 0.0500 e ce ee we ee 284; 87 
Semioxamazine, preparation > 3.6 ois ces vl Oe ess Bev ae 2 Oe 
SOONG eS haa cies 5a 6s hs ERR ORGANS DEE eee ae ee 
SEY oP Care ae Sar MPP iar rae Se ite can aN ae OMCs 20 
OM ro Ces hows a kewaeduv doe Gok ee ete ieee 22, 23, 31 
AE es Sk hie ee BAR dd Lia es 49 
PAS neo e a dene ie Chee aed eel ot eee 81 

RPMI ee ree ha Sa oe sy tdg, iy aca eg ew, Se 35, 36 
IRIN Ee hss ia ates oh hd Ok AA ee a 
SS ae Hts bien Cede eee ee 
hydroxide, divdenivais by. oa ee aerate Sed aces II, 12, 109 
SOLOMMAE WE oases ANS he be eeER OE ee Le 107 
SPORE es ios ac cc AEE Ae ae De ATE Ae ee eee eee 52 
Seg: Sean ai ey ae aS ar a geha C eG ENPLS Ge a UM eS DN eS 129 
SIGHOMIE. 8s. Fo bile Ard be Sa OEE le Ra eee ek wl east 109 
A Ay a ROE ty ear era ga 2 en) eras tex ee nace emaNe roe. ey 
SUMNER LOTIGG. sos oe ooo aaa oe Ee Oe en CS 9 
SPOPRP EE BRNV ORME rig ees a ae ee a 30 
WRONG TEE aoa Soi a en gad We ce Re ua a 28 
SMONNOE 8 ios Ga ne ce Sees Bae eee We as oe BRE OR 54 
Subetitited benzoic acide. 90. ii oo ee as 26 
SCVIATION BY. 6 os. a. SS 27 

phenylhydrazones, preparation............. 73,74 
PUGPOLOURH, ff iis coe Bos De a 26, 109, I10, III 
Sulphuric acid, hydrolysis by...................11, 16, 110, III 
IGEN OT Te 66 Fad ce EEN Re ES eee 129 

é5 
TOONS eis ASN Oe ee Ra Ge ee 142 et seq 
Table for value of nde MTS Lic oe Bate a Be Ts 144 
oo —a 

of tension of benzene and water.................00+. 77 
water.. Ge ig tebe a Wao War © wae bey Oe a 


weight of a cc. of hydrogen igi aa cee yay wen tek 142 


INDEX. 161 


PAGE 
Daehn Peers cueing 6 ok MOS ee See eb RE EP a OO 
DCRR od Bie Og ee paneer ahd CRY Avis PACH Ee ace e Oe REE 9 
TP BSSINGT ce gos cate Rati ee er as OR aT RE RE aera gO 
(LetsaDrompneny DY AraAZInG 65 5535 eaenr nso yebieos Hee rent 74 
aoracetic acid«as acetyiating agents... ccs bev sos es 9 107 
AO) 5 1 ee ee eke FURAN ye SUNT ee oy NEN oe a eT 84, 85, 86, go 
Thiosemicarbazine derivatives, preparation.............. 88 
TROVE ONES Fee aes ee ee Rey gk ise ge Ia NR 27 
DNOUES org ete: oho OS. Wie taut oP ate a9 bu Iw eee ears eae 70 
TOV PRcER dtd cpeeivin’s sitere aed oh Ow Er em GaN he oe een as aes ae 81 
PACKARD ot ay Oe AES See R i EAE aE Oe Raa 106 
PACIRGHN Eee oe Ri Lak ee es re Na ee 73, 81, 82, 87, 88 
PA Be I Ro cs hein ook a RIAL Fa as RL ER EDO 
Pe RSIOD EE SP a et Ts 5290, 04 
‘hibrationsOr acids, 7 a Ae eee ai Sear Skee 48, 50 
P-Talnenestipnomcchlonide vaio. onc oe a noes Se 107 
s-Pribromphenylhy drazine woc 5c ae ee ee ew sre Oe 
ESCHUPOET , Dine scien ade! ae esis Ge oN Sees re ee 37 
U 
MAN Poo Be ee ee re ORO ae Cetin wea kietee hen 32, 108 
ULTRA DAS Nae ae eget ah dey pie aE Mesh hes CaP aero a yO 12 
ORZOR SICK © oa cad Sate Gee tae as Sige AU a eee Medeor go 
V 
Vi GLA GHEs hcis ci os ork Gree a RGR Sees OA ale ORR ERG RE wk 53 
ALB er Poe ona nee enn yale aan eee ha eee ee aah 9 
VRID eee icra hy Si ee ee ALC MSS Cee aes ang ee 135 
Vielleger Vo eg delta cess a FOO eee Oe ee ae 106, 136 
VOWEL Fe AN aoe tek Sid Sank wre tei tarts cen RG Hh ve UR ee Nee ei 59 
WORT: Sem nue eR eee eae ue ewe 47; 81; 137 
VORSONICRICN ais cat Ooce Sasa sae cake eae FOL SD 
VOTO ORO a ie eon Sih iw it Oe Med er eee 13 
WPGC rs ak eta ae. te ee ee ee ee ce 125 
WwW 


WENO rica ere aan Gn ee aoe ks Sod REN er eee aha Toe 


162 INDEX. 


PAGE 
WORK ASF, sn Stare os ee REE eR Shean oe ae ae 
WOOD RI or  BNes See Rak OU ee ii ose oa 110 
WGN Fick cen Cee at COR See ERG es eae ens 132 
Water and benzene, table of tension. .................00- 77 
BY Grolysis DY. sessile deka a be be OR ES eve a dea 
eerie Of LenSiON : co0N oe, Se NG as eS 144 
PURGE NY occ ow bie soe se sD ey ES OE DSR EO wees 70 
WCF 2 Seis oss ea 32, 108 
RP RREE Peo ens sie 5 Va aw ses Ope NLR Ee Se rag 16 
TU NOIRE, oii oo 85 Fossa ore iN eben Hos RARE OEE 57 
PUMICE Oe § cain Gem dn aid Slee gta gilda hus ho Soo 8 be BOO 137 
Pe RGN Royo ag is pe Foe Ke Aa A Ee 135 
DOR PMNS Br os Cosa HON a eee eae 6 Fe ON ESS 9, 18, 37; 79 
WU Lee a Se ivs oho SCAR AW EE Bk 80 
WO eee hile oS chin ss Ge EES wR ee aN ae 92 
Wright 12 
¥. 
COMME Ws y's ah as be 5 REG re sian ale seb nee o bab ne eases 129 
Z 
Zanoli..... Sra Kis Wik Sr rd Sia AR Se ca! SPS aah CAG ache eee 35 
LEE See GA CE ie 8 2,12, 14, 32, 38, 44, 45, 48, 83 
LOUSCHAL HO Sa ig eS a EU Bk DE Oe a IOI 
Pes ES 5 Ba), Cee apap manne inet aves Car ier ee: Ce ee en 88 
LARC CRICHAE oss oh 8 SS "yk Mab OS Ware eee Rie lee A 9 
dihydroxylamine hydrochloride, reagent for car- 
DODGY es ors aa 58 COR aoa Ree J Wace eegeep eae 80, 83 


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Rostoski’s Serum Diagnosis. (Bolduan.)............-..-+2--4----- 12mo, 
Ruddiman’s Incompatibilities in Prescriptions.............-.--++-++e+++- 8vo, 
Sabin’s Industrial and Artistic Technology of Paints and Varnish........ 8vo, 
Salkowski’s Physiological and Pathological Chemistry. (Orndorff.)....8vo, 
Schimpf’s Text-book of Volumetric Analysis.............- a aehines @ .I2mo, 

Essentials of Volumetric Analysis............- pa cd nen gene ge cca las 
Spencer’s Hanabook for Chemists of Beet-sugar Hoeses. wee 16mo, morocco, 

Handbook for Sugar Manufacturers and their Chemists. .16mo, morocco, 
Stockbridge’s Rocks and Soils...... iki acen gure ddeitlcn Seceewn dened s sie 


* Tillman’s Elementary Lessons in Heat.........-.sscececcccccccecs BVO, 
» Descriptive General Chemistry... ......22cscccccccceccccccces sBVOs 
Treadwell’s Qualitative Analysis. (Hall.)...........cccecccee cde e ees BVO, 
Quantitative Analysis. (Hall.)........... Soévewn vaduanitas6eseeeeey 
Turneaure and Russell’s Public Water-supplies............. Jebhessnacsve 
Van Deventer’s Physical Chemistry for Beginners. (Boltwood. \serrre 
* Walke’s Lectures on Explosives................-.e-- apicin ass ob ecic ae ee 
Washington’s Manual of the Chemical Analysis of Rocks.............. 8vo, 
Wassermann’s Immune Sera: Hemolysins, Cytotoxins, and Precipitins. (Bol- 
ENC eng Meee ey er Lala rage ate ace se 616 RG semis 6 6 ©, ejel¢,¢/6,0.0% I2zmo, 

Wells’s Laboratory Guide in Qualitative Chemical Analysis............. 8vo, 
Short Course in Inorganic Qualitative Chemical Analysis for Engineering 
Srlenian..5). «cuniise oede caaes gid RM die: ¢ du cieWie swe we = + sve Kasies 
Whipple’s Microscopy of Drinking-water...........-.-++++eeeee+++---8¥0, 
Wiechmann’s Sugar Analysis........... sina dede tee caiceiwidwid’s - « SR Sap, 


Chlorination Process eeee eeeneeeeeeoe ee ee ewe eeeee eee eeeneeneeneee I2mo, 
Wulling’s Elementary Course in Inorganic Pharmaceutical and Medicai Chem- 
istr y ere #ee@ eee ee eeeeeeeee © eeeeeneeeeee ee ee@eeeee ee ee een eee I2mo, 


CIVIL ENGINEERING. 


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BRIDGES AND ROOFS. HYDRAULICS. MATERIALS OF ENGINEERING 


RAILWAY ENGINEERING. 


Baker’s Engineers’ Surveying Instruments. ............c2eccesceecees I2mo, 
Bizby’s Graphical Computing Table............... Paper 194 X 24} inches. 
=* Burr’s Ancient and Modern Engineering and theIsthmian Canal (Postage, 
ap Cents BddIOERAE) foes eos Fae Sok eh eee ceee «tee cocec ct¥O, Net, 
Comstock’s Field Astronomy for Engineers........... cee ceccecceeces BVO, 
Davis’s Elevation and Stadia Tables.................. btcnawatbceene sane 
Eliiott’s Engineering for Land Drainage..... ESRD Ra cad euoeb ac eu ec cemeeuna 
Practical Farm Drainage.............. Ridlawae oo kboee oas.e 6pe.ae RAPS 
Folwell’s Sewerage. (Designing and Maintenance.)............ ...+--8¥0, 
Freitag’s Architectural Engineering. 2d Edition Rewritten....... 2202 SVC. 
i te oes cco ceca ss ccaes cas 66 cee cdl encase seers 8vo, 
Goodhue’s Municipal Improvements................--ceececcceeees I2mo, 
Goodrich’s Economic Disposal of Towns’ Refuse. .........-...---.---- 8vo, 
Gore’s Elements of Geodesy. .............. 222s eceeeees esanign te cobs 8vo, 
Hayford’s Text-book of Geodetic Astronomy................--..-+--:; 8vo, 
Hering’s Ready Reference Tables (Conversion Factors),......16mo, morocco, 


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Howe’s Retaining Walls for Earth............. ate aay cope eins I2mo, 
Joknson’‘s (J. B.) Theory and Practice o1 Surveying. Sha nha 4 see ree Small 8vo, 
Johnson’s (L. J.) Statics by Algebraic and Graphic Methods............ 8vo, 
Laplace’s Philosophical Essay on Probabilities. (Truscott and Emory.) 12mo, 
Mahan’s Treatise on Civil Engineering. (1873.) (Wood.)............ 8vo, 
© :Deactiptive Geomeuy $c. >. -~ t5 ce ws. eh ek ne + sik nak oon 8vo, 
Merriman's Elements of Precise Surveying and Geodesy........ ais aaa 8vo, 
Elements of Sanitary Engineering. ............ cece ccc ccc cccce 8vo, 
Merriman ard Brooks’s Handbook for Surveyors.............16mo, morocco, 
Nugent’s Plane Surveying..............ceecceees 5 ip ia a bhik aaa eo ee 8vo 
Ogden’s Sewer Design. ...............000- ies atawline dake ae I2mo, 
Patton’s Treatise on Civil a Seg 5b igs Mish ch Scnlaiete eR ath ee 8vo half leather, 
Reed’s Topographical Drawing and Sketching. ..............cecececece 4to, 
Rideal’s Sewage and the Bacterial Purification of Sewage....... as en aot 8vo, 
Siebert and Biggin’s Modern Stone-cutting and Masonry................ 8vo, 
Smith’? Manua! of Topographical Drawing. (McMillan.).............. 8vo, 
var mye Graphic Statics, with Applications to Trusses, Beams, and 
seen Ree ht RP Rr peep Reka onl gt peg ipeen alii aaa nctica VO, 
Taylor and Thompson’s Treatise on Concrete,Plain and Reinforced. (In press. 
* Trautwine’s Civil Engineer’s Pocket-book................ 16mo, morocco, 
Wait’s Engineering and Architectural Jurisprudence................. i 
eep, 
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Sheep, 
SAW OF CIE. 0, bs ss pine kha aaa Ac toh oes oS ules de iak ts De a 8vo, 
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Webb’s Problems in the Use and Adjustment of Engineering Instruments. 
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* Wheeler’s Elementary Course of Civil Engineering................... 8vo, 
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BRIDGES AND ROOFS. 


Boller’s Practical Treatise on the Construction of Iron Highway Bridges. .8vo, 2 
* Thawte River: Bridge. esse seis c ASE 4to, paper, 5 
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Du Bois’s Mechanics of Engineering. Vol. IL. pins tide oth alicia a RE TES Small 4to, 10 
Foster’s Treatise on Wooden Trestle Bridges.........0220+-eeeegseeeee 4to, 5 
Fowler’s Coffer-dam Process for Piers... ........cc0cececeees Bie e\ele bets 8vo, 2 
Ordinary Foundations. .: 45: siies is HA CET es 8vo, 3 
Groaie’s Book Traseen i. xin i saws Gaidiee bn Colic £ Vane ebeds see Maken 8vo, I 
WTIGSS LLU. . 66k cis eens kene ee EE OO ET POT 8vo, 2 
Arches in Wood, Irom, and Storie ss 6665 wisi nas onan 6 eho dined bead 8vo, 2 
Ho We's. TRORUSS OD ARCHAG, 05 65 555 vx BN Ccds LAUREL p band Ka Ve dean 8vo, 4 
Design of Simple Roof-trusses in Wood and Steel.................. 8vo, 2 
Johnson, Bryan, and Turneaure’s Theory and Practice in the Designing of 
Modern Framed Structures...........-.cccccccceees S 4to, 10. 
Merriman and Jacoby’s Text-book on Roofs and Bridges: 
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Part 3i-STAO IC DURTOB: 5 6:0 k 0 0 scdes 6 wh a cles bb Rae oes 8vo, 2 
Part IIIl.—Bridge Design. 4th Edition, Rewritten........... Bee: 8vo, 2 
Part Feo E eer SU UCUMIORs cas cs caneinekl bac mds bam sie de kane noe 8vo, 2 
WMoriaon’s Mempus Bass, . 6.5550 cc cs bs y ese tee kes bak ho aah ake 4to, 10 
Waddell’s De Pontibus, a Pocket-book for Bridge Engineers...16mo, morocco, 3 
Specifications for Steel Bridges. 2.2.2... csc c eee e cece cc ccsceeces 12mo, I 
Wood’s Treatise on the Theory of the Construction of Bridges and Roofs.8vo, 2 
Wright’s Designing of Draw-spans: 
Part I, —Plate-girder Draws.........-cccceecsccecees Se pas nek 5 ce 
Part II.—Riveted-truss and Pis-conkectel Long-span ‘Desa Peek ers 8vo, 2 
3 


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HYDRAULICS. 

Bazin’s Experiments upon the Contraction of the Liquid Vein Issuing from an 
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Church’s Mechanics of Engineering...... a item adem eda PyPrr eer ee 
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Flather’s Dynamometers, and the Measurement of Power............. I2mo, 
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Peoctesé Water and Public Hoan. 2.65. occ ec cccadcwccsccvcess I2mo, 
Wee ration: WOERD. 6.5 oo ni icc cccccccccases PER Pe ree I2mo, 
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Mason’s Water-supply. " (Considered Principally from a Sanitary Stand- 


HOLGE ) SE WG aas,; MOT Ss ai. ook Soa Snes ccccccccas és eNO 
Merriman’s Treatise on Hydraulics. oth Edition, Rewritten...........8V0, 
® Michie’s Elements of Analytical Mechanics. ->................2-.0--- 8vo, 
Schuyler’s Reservoirs for Irrigation, Water-power, and Domestic Water- 

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Turneaure and Russell’s Public Water-supplies. ............ ¢ennkeaene 8vo, 
Wegmann’s Design and Construction of Dams..............0-e2eeeee0- 4to, 

Water-supply of the City of New York from 1658 to 1895..... Sureiviaras aie 
Weisbach’s Hydraulics and Hydraulic Motors. (Du Bois.)............. 8vo, 
Wilson’s Manual of Irrigation Engineering..................-- Small 8vo, 
Wolff’s Windmill as a Prime Mover... ...... cece cece cece e cece cece sBWOs 
OU ONO wdc co lakns cad owiwswess> awe chee swn its. gin ela tall aievs 8vo, 

Elements of Analytical Mechanics... . 2.2... ccccccccccccccccees 8vo, 

MATERIALS OF ENGINEERING. 
Baker’s Treatise on Masonry Construction.............--020--eeecees 8vo, 

Roads and Pavements..................- a wie ole ect ieinie ices tace arate 8vo, 
Black’s United States Public Works...................0202 % .Oblong 4to, 
Bovey’s Strength of Materials and Theory of Structures................. 8vo, 
Burr’s Elasticity and Resistance of the Materials of Engineering. 6th Edi- 

Cit, MOWEUG.. 5 a cle dewdvccdievooaee ees Uae Suede s las 8vo, 

MyINe's MIU OST COUMCUCUOR S66 ccc cicedecceerws ces cuescouwatcsws 8vo, 

Inspection of the Materials and Workmanship Employed in eerreanes 
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Charch’s Mechanics of Engineering < oo éiiiic dé ce cccecewcedccceccscecc. 8vo, 
Du Bois’s Mechanics of Engineering. Vol. Sarena 4to, 
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Parwminn ys Ureinary BOUNGAMONS, 6 oo as 5 5 455s 6k 5 cals os ye abate oe rier 8vo, 
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REISE Fe PEOCTRINES Fo 5s on cS kk alle Ge oda calls qaVecerunes< 8vo, 
Martens’s Handbook on Testing Materials. (Henning.) 2vols......... 8vo, 
Merrill’s Stones for Building and Decoration..............-2-ececeee-- 8vo, 
Merriman’s Text-book on the Mechanics of Materials................. 8vo, 

SOUR MRIMEC RY Oe SITES ons cg ww phe Guat hc sete wcmebeee oes I2mo, 
Metcalf’s Steel: A Manual for Steel-users. .. ... 2.5.5.2 oc tee ce ecee I2mo, 
Patton’s Practical Treatise on Foundations...................eee-00-- 8vo, 


Richey’s Handbook for Building Superintendents of Construction. (Jn press.) 
Rockwell’s Roads and Pavements in France, .,.,...eeeceserereseee +I 2M, 
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Sabin’s Industrial and Artistic Technology of Paints and Varnish...... 8vo, 


Smith’s Materials of Machines...) 6 3 Ps SVE FE WE SR RS I2mo, 
Snow’s Principal Species of Wood... 0... icc ee cee eee eee ee es BVO, 
Spalding’s Hydraulic Cement, ....... 0. cette eee re eee sence I2mo, 

Text-book on Roads and Pavements...........00000ce ee eeeeeee I2mo, 

Taylor and Thompson’s Treatise on Concrete, Plain and Reinforced. (Jn 

press.) 

Thurston’s Materials of Engineering. 3 Parts.................20.008- 8vo, 
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Part III.—A Treatise on Brasses, Bronzes, and Other Alloys and their 

WGA UGOHIRs Fi GER ROO eae 4 as Obes ares cone ee Ree 8vo, 

Thurston’s Text-book of the Materials of Cobatwuclide See eae Waser cla te 8vo, 

Tillson’s Street Pavements and Paving Materials. ....................- 8vo, 

Waddell’s De Pontibus. (A Pocket-book for Bridge Engineers.)..16mo, mor., 
Specifications for Steel: Bridgess.c 6.0% eS i oli ei Oe ee Bae I2mo, 

Wood’s (De V.) Treatise on the Resistance of Materials, and an Appendix on 
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Wood’s (De V.) Elements of Analytical Siichiaion, kaa St <i. Bae NeS 8vo, 

Wood’s (M. P.) Rustless Coatings: Corrosion and Electrolysis of Iron and 
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RAILWAY ENGINEERING. 

Andrews’s Handbook for Street Railway?Engineers..... 3x5 inches, morocco, 

Berg’s Buildings and Structures of American Railroads....... Rea Seeds oe le 4to, 

Brooks’s Handbook of Street Railroad Location............ 16mo, morocco, 

Butts’s Civil Engineer’s Field-book..............c0eee cece: 16mo, morocco, 

Crandall’s Transition Curve.......... Eid G, We ORR ISe teas ee eee morocco, 

« Railway and Other Earthwork Tables................------0-- 8vo, 

Dawson’s ‘‘Engineering”’ and Electric Traction Pocket-book. 16mo, morocco, 

Dredge’s History of the Pennsylvania Railroad: (1870).............. Paper, 

* Drinker’s Tunneling, Explosive Compounds, and Rock Drills, 4to, half mor., 

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Howard’s Transition Curve Field-book.. .................. 16mo, morocco, 

Hudson’s Tables for Calculating the Cubic Contents of Excavations and Em- 

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Molitor and Beard’s Manual for Resident Engineers. ................ 16mo, 

Nagle’s Field Manual for Railroad Engineers............... 16mo, morocco, 

Philbrick’s Field Manual for Engineers.......... Pes aralgit ay 16mo, morocco, 

Geariests: Field. Ungineering. sa iag choc cc kc cor seve shes ess an 16mo, morocco, 
Railroad Spiral........ Lhe ODES Fda eas oie mitch 16mo, morocco, 

Taylor’s Prismoidal Formule and Earthwork. ...........-.---eeeeeee 8vo, 

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Embankments by the Aid of Diagrams. ..................... 8vo, 


The Field Practice of Laying Out Circular Curves for Railroads. 
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Wellington’s Economic Theory of the Location of Railways...... Small 8vo, 
: DRAWING. 

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MBOrBe Fs SE aa He PES a ee ae Oblong 4to. 


Durley’s Kinematics of Machines. ................- CO ei ahah Blick SONOS 


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Hill’s Text-book on Shades and Shadows, and Perspective..............8Vvo. 


Jamison’s Elements of Mechanical Drawing. ...................00--- 8vo, 
Jones’s Machine Design: 
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MacCord’s Elements of Descriptive Geometry. ... ..............-.000- 8vo, 
Kinematics; or, Practical Mechanism. ...................0-000-- 8vo, 
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MEO DIGSTOIINGES 568. eine Bie db PUN Sole cides oC Ete b s OO > of 8vo, 
Mahan’s Descriptive Geometry and Stone-cutting.................... 8vo, 
ceincrral Drawin: CPMOMMPOON: 5 a. co ce ecco cecenescece 8vo, 
Moyer’s Descriptive Geometry. (Jn press.) 
Reed’s Topographical Drawing and Sketching.............. ma arazaieieta eee 4to, 
Reid’s:Cousse‘in Mechanical Drawing. .... 2... . 0 ecw ccc ccc ccccee: 8vo, 
Text-book of Mechanical Drawing and Elementary Machine Design. .8vo, 
Robinson’s Principles of Mechanism. ..............-.... eee eeeeeeee- 8vo, 
Schwamb and Merrill’s Elements of Mechanism........... Beg Sig ee aire xt 8vo, 
Smith’s Manual of Topographical Drawing. (McMillan.).............. 8vo, 
Warren’s Elements of Plane and Solid Free-hand Geometrical Drawing. .12mo, 
Drafting Instruments and Operations. .................-.-+---- I2mo, 
Manual of Elementary Projection Drawing..................... I2mo, 
Manual of Elementary Problems in the Linear Perspective of Form and 
SIMON Ss oreo am ais earns Be Sao eEtaOd Sean PIE A aos oe eelommeie ais I2mo, 
Plane Problems in Blementary Geometry. ...................-. I2mo, 
LUNOEE CGOTIBIE Tie 6 reno os tis hae Se lo ck ae eae * I2mo, 
Elements of Descriptive Geometry, Shadows, and Perspective...... 8vo, 
General Problems of Shades and Shadows.................-.2-2.. 8vo 
Elements of Machine Construction and Drawing.................. 8vo, 
Problems, Theorems, and Examples in Descriptive Geometry....... 8vo, 
Weisbach’s Kinematics and the Power of Transmission. (Hermann and 
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Whelpley’s Practical Instruction in the Art of Letter Engraving....... I2mo, 
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Wilson’s (V..T.) Pree-hand Perspective... . .. oc ccccicccccccpecccccccces 8vo, 
Witsoh’s CV7:) Freehand. Lettering: so20503 oS so as. xae cawsewaws<ses « 8vo, 
Woolf’s Elementary Course in Descriptive Geometry ............ Large 8vo, 
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Anthony’s Lecture-notes on the Theory of Electrical Measurements. ...12mo, 
Benjamin's: Historyof Blectsinitye <ccnsk aici oleic dee ewe senses oes ows 8vo, 
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Classen’s Quantitative Chemical Analysis by Electrolysis. (Boltwood.). .8vo, 
Crehore and Squier’s Polarizing Photo-chronograph. .................. 8vo, 


Dawson’s “‘Engineering”’ and Electric Traction Pocket-book. .16mo, morocco, 
Dolezalek’s Theory of the Lead Accumulator (Storage Battery). (Von 


MNO ee oo oe ve Ae OL yore 4 SO ew a SUN WE Oe Ea ele I2mo, 
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Gilbert’s De Magnete. (Mottelay.)....... Bie Sik ahd lat & aia ee eho wigan case SS 8vo, 
Hanchett’s Alternating Currents Explained........................-. I2mo, 
Hering’s Ready Reference Tables (Conversion Factors)...... 16mo, morocco, 
Holman’s Precision‘of Measurements... 2. 56. osc eo be ee 8vo, 

Telescopic Mirror-scale Method, Adjustments, and Tests... ..Large 8vo, 
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Liéb’s Electrolysis and Electrosynthesis of Organic Compounds. (Lorenz.) t2mo, 
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® Lyons’s Treatise on Electromagnetic Phenomena. Vols. I. and II. 8vo, each, 
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Ryan, Norris, and Hoxie’s Electrical Machinery. Vol. L................8V0, 


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Tory and Pitcher’s Manual of Laboratory Physics....... eceese- mall 8vo, 
Ulke’s Modern, Electrolytic Copper Refining .,.......eeeceeecvesss -BVOy 
LAW. 

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» Treatise on the Military Law ot United States............0.0-.-- 8vo, 
* Sheep, 
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Wait’s Engineering and Architectural Jurisprudence..... iwecuek eee: habe 

CeD, 


Law of Operations Preliminary to Construction in Engineering and Archi- 


CBOE Ee OS eC UROL CSS le tle Shoes beens cases cetewey 
Sheep, 
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Encyclopedia of Founding and Dictionary of Pountry Terms Used in the 
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Effront’s Enzymes and their Applications. (Prescott.).........c.ceccee-- 8vo 
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Ford’s Boiler Making for Boiler Makers. ...........cccccccccccceces 18mo, 
Hopkins’s Oil-chemists’ Handbook...... vie dee a pele ska a ase Mais 40k CT 
BGO WH GOR BPR tench cdeccdcicvbd cur as sedhee bes coke cone sake cake 8vo, 


Leach’s The Inspection and Aualssla of Leal with Special Shidancs to State 
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Meyer’s Modern Locomotive Construction. ...... AeA aR GA: Game SAL EEE ge 4to, 
Morse’s Calculations used in Cane-sugar Factories. .........16mo, morocco, 
* Reisig’s Guide to Piece-dyeing........... cc ccc cece cc cece cccecccee 8vo, 
Sabin’s Industrial and Artistic Technology of Paints and Varnish ...... 8vo, 
Smith’s Press-working of Metals............e0ccgecsccccccccees cess sBVOy 


Spalding’s Hydraulic Cement..... eee csec seb bobess sb éuveeeternsds : i: t3me, 
Spencer’s Handbook for Chemists of Beet-sugar Houses... ..16mo0, morocco, 

Handbook for Sugar Manufacturers and their Chemists...16mo morocco, 
Taylor and te yeni Treatise on Concrete, Plain and Reinforced. (Jn 


press. 
Thaurston’s Manual of Steam-boilers, their Designs, Construction and Opera- 
CMON FONG dc vnc veRik date ckuewe EE PES EES PRTG Fee ry te eee 8vo, 
* Walke’s Lectures on Explosives.......ccccccccccccccccccscecsecs . .8vo, 
West’s American Foundry Practice..........ecseceee. sists se aueiw doi 12mo, 


Moulder’s PY ce) Cee te pe Ow rere eee er re ey eT Ree oe 


10 


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Wolff’s Windmill as a Prime Mover...... ie Geswweae Cicoc dw cecceastes 


Woodbury’s Fire Protection of Mills. ............2..2 eee eeeeeeeecees 8vo, 
Wood’s Rustless Coatings: Corrosion and Electrolysis of Iron and Steel. . .8vo, 
: ; MATHEMATICS. 

Dalene es Meee WORCTONS, . cc cuvccccccccccccccccrscccccccassscsncs 8vo, 
® Bass’s Elements of Differential Calculus............c2cccececeeees 12mo, 
Briggs’s Eiements of Plane Analytic Geometry.............--. aaa was I2mo, 
Compton’s Manual of Logarithmic Computations..... wens Se wow ses I2mo, 
Davis’s Introduction to the Logic of Algebra....... Si eeaaaeeeWetEees 8vo, 
® Dickson’s College Algebra.................. Seer fire eee Large 12mo, 
@ Answers to Dickson’s College Algebra. .........220- Aare 8vo, paper, 
# Introduction to the Theory of Algebraic Equetioos San /aiaisi Large 12mo, 
Halsted’s Elements of Geometry........ a cielo wien ncune pala a kalaie’s Seis 8vo, 

Elementary Synthetic Geometry...... eger ge walneplantcemeaaase icine 8vo, 

Matiqnal Geometric soso s ow ce ca ed acces gees cnceenSaieceeecien = I2mo, 


* Johnson’s (J. B.) Three-place Logarithmic Tables: Veub-pockst size. . paper, 
100 copies for 
* ' Mounted on heavy cardboard, 8 X ro inches, 


* 


‘ 10 copies for 
Johnson’s (W. W.) Elementary Treatise on Differential Calculus. . .Small 8vo, 
Johnson’s (W. W.) Elementary Treatise on the Integral Calculus. .Small 8vo, 
Johnson’s (W. W.) Curve Tracing in Cartesian Co-ordinates.......... I2mo, 
Johnson’s (W. W.) Treatise on Ordinary and Partial Differential Equations. 

Small 8vo, 
Johnson’s (W. W.) Theory of Errors and the Method of Least Squares. .12mo, 
* Johnson’s (W. W.) Theoretical Mechanics.......................- I2mo, 


Laplace’s Philosophical Essay on Probabilities. (Truscott and Emory.) 12mo, 
* Ludlow and Bass. Elements of Trigonometry and Logarithmic and Other 


SEM Sear ae ote ec chats Sept ila tigi a aidieiese Ge bie elaialeie aie o’se-aNe 8vo, 
Trigonometry and Tables published separately................ Each, 

* Ludlow’s Logarithmic and Trigonometric Tables ...................-- 8vo, 
Maurer’s Technical Mechanics................-- wae a eeteats senate a avaveats 8vo, 
Merriman and Woodward’s Higher Mathematics .......... emia sche eats 8vo, 
Morera 6 eted of Leonel Shears oi. 4 oes svc ced Soanccccscescccccas 8vo, 
Rice and Johnson’s Elementary Treatise on the Differential Calculus.Sm., 8vo, 
Differential and Integral Calculus. 2 vols. in one.......... Small 8vo, 
Wood’s Elements of Co-ordinate Geometry............ Sewadalenseecaas 8vo, 
Trigonometry: Analytical, Plane, and Spherical................. I2mo, 


MECHANICAL ENGINEERING. 
MATERIALS OF ENGINEERING, STEAM-ENGINES AND BOILERS. 


Bacon’s Forge Practice........ ee ke eae fr inahawedetaewicsceudessiss 12mo, 
Baldwin’s Steam Heating for Buildings. ..... tio secs eG cetlek Sad ees 573 I2mo, 
Barr’s Kinematics of Machinery......... Siplniata salvia oleic co W806. wia'es site inie 8vo, 
Pari © Mechanical Drawitie 5 65 so sae Se hes ewe decicbecids 8vo, 
e = > ” MPG BS Ss Soo onc cavcncccceeets 8vo, 
Benjantin's Wrinkles and Recipes. ~ . 2.2.2. c ccc ccc ccc cc ccc cc cece I2mo, 
Carpenter’s Experimental Engineering................ ib eeeacnect es 8vo, 
Heating and Ventilating Buildings.......................-20000- 8vo, 
Cary’s Smoke Suppression in Plants using Bituminous Coal (Jn prep- 
aration.) 
Glork’s Gas and Oil Bogine....... ..occccccccacsccee wemuie Seah Small 8vo, 
Coolidge’s Manual of: Drewime oasis 5. oo5 66k 5 nse idk 0c otc ces 8vo, paper, 
Coolidge and Freeman’s Elements of General Drafting for Mechanical En- 
gineers, ..... &, 0:5 RAN OS ,ai ds, a MEDORA S Ge ate Rice +eere+,- Oblong 4to, 


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Cromwell’s Treatise on Toothed Gearing.....-......--s-se00- ois Se wie RRMNO, 


Treatise on Belts and Pulleys.......ccccccccccscceccccece 5 sek vlSMO, 
Durley’s Kinematics of Machines. .............0-00-e eee. Rksdets uta 8vo, 
Flather’s Dynamometers and the Measurement of Power........... ..I2mo, 

Rope Driving. 6. csc cece cps eeev saa vebeeewres ae Ne y 
Gill’s Gas and Fuel Analysis for Engineers............. Oper ore er I2mo, 
Hait’e Car Lubrications 35 6s-eo 8 6os ss soa 358g oh a es we alais wae I2mo, 
Hering’s Ready Reference Tables (Conversion Factors)...... 16mo, morocco, 
Hutton’s The Gas Engine........... Sn dink Se Ke SPE TE SMACK S Ce eRe See 8vo, 
Jamison’s Mechanical Drawing, 5. ices 0s corsa er 825 a PRA ee bbe s he 8vo, 
jJones’s Machine Design: 

Part I.—Kinematics of Machinery.............cecccccecececess 8vo, 

Part Il.—Form, Strength, and Proportions of Parts................ 8vo, 
Kent’s Mechanical Engineer’s Pocket-book. ........--ese00:% 16mo, morocco, 
Kerr’s Power and Power Transmission. .........-...-ee0- eats eames Svo, 
Leonard’s Machine Shops, Tools, and Methods. (Jn press.) 

MacCord’s Kinematics; or, Practical Mechanism............... aneme's forte 
Mechanical Drawing........... Ne tea Et Bip ty 1 2 Sa ceetees once 4to, 
VOROGEEy SR ine Aone Se ekee eats ese evens Rey eee ety 8vo, 

Mahan’s Industrial Drawing. (Thompson.)......... cease seed ness esas 

Poole’s Calorific Power of Fuels............. cece ccecececccee 5 tiecea see 8vo, 

Reid’s Course in Mechanical Drawing..............-cccccccccesccees 8vo, 
Text-book of Mechanical Drawing and Elementary Machine Design. .8vo, 

Richards’s Compressed Air........... OR Lala Nee Nh es SEER Rega deh SEES I2mo, 

. Robinson’s Principles of Mechanism................-6- Si vvie ewe peters 8vo, 

Schwamb and Merrill’s Elements of Mechanfsm...................0005 8vo, 

Bosith’s Preas-Working Of BOs «0.5 6s). cncnctnaws saeeb 0900500 Ne wes ons 8yvo, 

Thurston’s Treatise on Friction and Lost Work in Machinery and Mill 

WROTE 35 reg kc Rieke obi ule te, Fhe Re Wine eo pie Us be vee PIS a och ie ods alt 8vo, 

Animal as a Machine and Prime Motor, and the Laws of Energetics.12mo, 
Warren’s Elements of Machine Construction and Drawing............... 8v0, 
Weisbach’s Kinematics and the Power of Trarsmission. Herrmann— 

DDE SGU, Saw eu sod winds ould ke BAS SY Oe 2 SACS Y OE Seve eee 8vo, 

Machinery of Transmission and Governors. (Herrmann—Klein.). .8vo. 

Hydraulics and Hydraulic Motors. (Du Bois.).............. BEERS oc: 
Wolff’s Windmill as a Prime Mover... ......cceccecencccccccccees .. .8vo, 
Wood’s Turbines............20-- SiGe ios Swed enn ae tees wirah cas vere, 

MATERIALS OF ENGINEERING. 
Bovey’s Strength of Materials and Theory of Structures................ 8vo, 
Burr’s Elasticity and Resistance of the Materials of Engineering. 6th Edition 
ROBB ics LEDC wes eee Seba buses eee Seb GAN wb ace woah 8vo, 

Church’s Mechanics of Engineering ..... bcbrd whetn ioc A ACLE Si, SRE A S Slowhaats 8vo, 

Johnson’s Materials of Construction....... Seveueclws eae eMnIen Large 8vo, 

Keep’s Cast Iron PSE Porc Se gee ae oh ay hv onebaeh-sa% o hilieind Seema te 

Lenza’s Applied Mechanics... 055). 5.0% 5s oo 00 ve aventione tes 4 sinbien 3 ONOe 

Martens’s Handbook on Testing Materials. (Henning.)............ ..-8V0, 

Merriman’s Text-book on the Mechanics of Materials..... pekawhes Pe cas .8vo, 
Strength of Materials «5655 ac .5s cae oy seed ba nis I2mo, 

Metcalf’s Steel. A Manual for Steel-users.............2.cccceeceees I2mo 

Sabin’s Industrial and Artistic Technology of Paints and Varnish...... 8vo, 

Gmith’s Materials of Machines «:6:c0ié sods Gece Ga WS <0 £6 bw ewaNe’s 12mo, 

Thurston’s Materials of Engineering..... ty Pere EP -----3 Vols., 8vo, 
Past’ TI. Tron and. Steaks sic ick ieee, 8vo, 
Part III.—A Treatise on Brasses, Bronzes, and Other Alloys ond their 

Constituesttn. o's sie 50k 3s JCC NS IE Wie EOL ER 8vo 


NUL Ww NUN HH NWP 


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50 


Text-book of the Materials of Construction. ....cssscoesceeceess sB¥O, 5 00 


12 


. 


—~ — 


Wood’s (De V.) Treatise on the Resistance of Materials and an Appendix on 


tite: Preservation:.of Timber... 5.355236 rE Sei nse acle toe Sex 8vo, 2 

Wood’s (De V.) Elements of Analytical Mechanics... .................. 8vo, 3 
Wood’s (M, P,) Rustless Coatings: Corrosion and Electrolysis of Iron and Steel. 

8vo, 4 


STEAM-ENGINES AND BOILERS. 


13 


a 


Carnot’s Reflections on the Motive Power of Heet. (Thurston.)....... I2mo, I 50 
Dawson’s “Engineering” and Electric Traction Pocket-book..16mo, mor., 5 00 
Ford’s Boiler Making for Boiler Makers............... 2 Eee ae 18mo, I 00 
Gons’s. Lecotiotive Sparks. . 2. ccc ccc cecicicccc ced ibesbor Pou pstsece: 8vo, 2 00 
Hemenway’s Indicator Practice and Steam-engine Economy.........- I2mo, 2 00 
Hutton’s Mechanical Engineering of Power Plants........ + TS 2-5 ee 8vo, 5 00 
Heat and Heat-engines....... snCUuReeaesesesasioeetecceseecoes 8vo, 5 00 
Kent’s Steam-boiler Economy................- AD Ee eet ee 8vo, 4 00 
Knease’s Practice and Theory of the lajector......... S'o8 coe Eaeva wens 8vo, I 50 
MacCord’s Slide-valves..... i wineries SeGe eee cab deb et CbWUS Ue ececces 8vo, 2 00. 
Meyer’s Modern Locomotive Construction re RARE ERS SRP PEP PP eC re a eee 4to, 1000 
Peabody’s Manual of the Steam-engine Indicator................... mz2mo, 1 50 
Tables of the Properties of Saturated Steam and Other Vapors...... 8vo, 1 00 
Thermodynamics of the Steam-engine and Other Heat-engines..... 8vo, 5 00 
Valve-gears for Steam-engines............ shee cdsbaacudiwccee ss 8vo, 2 50 
Peabody and Miller’s Steam-boilers ..... Eats e CREM ERE RIVE Tee E RES 8vo, 4 00 
Pray’s Twenty Years with the Indicator.....................4.. Large 8vo, 2 50 
Pupln’s Thermodynamics of Reversible Cycles in Gases and Saturated Vapors. 
(Oster SPE PE ie Po ie ares Per Ce eee ee 12mo, I 25 
Reagan’s Locomotives: Simple, Compound, and Electric.............. I2mo, 2 50 
Rontgen’s Principles of Thermodynamics. (Du Bois.).......... e++---8V0, 5 00 
Sinclair’s Locomotive Engine Running and Management...... aensecssRRMO, 2:00 
Smart’s Handbook of Engineering Laboratory Practice...............I2M0, 2 50 
Snow's Steams hollet Prveticss va cdc cece ccccccccccccccc ctsges.grdanie.D0O, 3 00 
DGS “VAS GORlS ios 65 os Chee S cdc Tec ccs ewes acvéedebay.ecees<OOA. 2:50 
Wotan on Thermod yaa ss 56 es. 56 oo 6566 iiie Foo ves ded dicts IZM) 00 
Spangler, Greene, and Marshall’s Elements of Steam-engineering........8vo0, 3 00 
Thurston’s Handy Tables........... § awouoe Vb Ss fades aweiddvcwm obnes 8vo, I 50 
Manual of the Steam-engine........... ic dmias di dw epee 2:WO.. S¥O, FO 00 
Part L—History, Structuce, and Theory...... phewaceiek’ Cacé-s.0.0< 8vo, 6 00 
Part I.—Design, Construction, and Operation. ................--- 8vo, 6 00 
Handbook of Engine and Boiler Trials, and the Use of the Indicator and 
the Prony Brake......... PGS Ai ce nite eth éeaie.s os\e,44 04 01% 8vo, 5 00 
Stationary Steam-engines. .......cccccereccccces Mas eewin s omele mess 8vo, 2 50 
Steam-boiler Explosions in Theory ant ds in Practice Ric sialars's ginal siete 12mo, I 50 
Manual of Steam-boilers, Their Designs, Construction, and Operation.8vo, 5 oo 
Weisbach’s Heat, Steam, and Steam-engines. (Du Bois.)............. 8vo, 5 co 
Whitham’s Steam-engine Design.............-.2-- Bere ets ee 8vo, 5 00 
Wilson’s Treatise on Steam-boilers. (Flather.) SRC selene Nels & welts Sees 16mo, 2 50 
Wood’s Thermodynamics Heat Motors, and Refrigerating Machines 8vo, 4 00 
MECHANICS AND MACHINERY. 
Barr’s Kinematics of Machinery... ...... 2.2.5... cc cceccccccccee <6 ss0D, 2.50 
_ Bovey’s Strength of Materials and Theory,of Structures................ 8vo, 7 50 
Chase’s The Art of Pattern-making........ Swale cule SiR GaE cla Coen sins I2mo, 2 50 
Chordal.—Extracts from Letters............ OnaKEES oe eC aES 5 SEs tN, 2°00 
Church’s Mechanics of Engineering..........ccccctccccccescesessss BVO, 6 00 


Church’s Notes and Examples in MechanicsS........cccccccccccccvces OVO, 
Compton’s First Lessons in Metal-working...........se+eeeese0+---I12M0, 
Compton and De Groodt’s The Speed Lathe.............2.s00++0++2-I2M0, 
Cromwell’s Treatise on Toothed Gearing................. cakickeh + 2a 
Treatise-on Belts and: Pulleys... ooc iss cnso-5 oso rs oe ae hayes ine ele 12mo, 
Dana’s Text-book of Elementary Mechanics for the Use of Colleges and 
Geno ca os CG a wed: S CEGIS a ao ta ee oe SRE Ee eee I2mo, 
Dingey’s Machinery Pattern Making.............2.cceseececececes I2mo, 


Dredge’s Record of the Transportation Exhibits Building of the World’s 
Columbian Exposition of 1893..........-......4to half morocco, 
Du Bois’s Elementary Principles of Mechanics: 


WOU eR AROMATICS, 6 ivinc.kib ewe 5 >» ciewialews eubiendd eho b00ceee coe 
Wh Sh ete. ss n'y bce bee pees Stews bh bekdaue bank ee 
Vea OP OR: ins bck eect ath inky hae ee abba bbenk wen 8vo, 
Mechanics of Engineering. Vol. I...........seseeee+----omall gto, 
Wok. Ta ci sans. pace Sink WE Small 4to, 
Durley’s Kinematics of Machines. ................00- sis Re es SR ce 
Fitzgerald’s Boston Machinist................+-ee0- inne See ++++--16M0, 
Flather’s Dynamometers, and the Measurement of Power............-12mo, 
PR ee a os ss Keowee 45,0 visits Suse ka i decide sestesaical oe++-I2MG, 
Dl a EGO R BORER oo 5 0-5 ¢ Habib swale eieeccecas canedecesicesctlee 
Hall’s Car Lubrication.......... ates devas ‘sida de 2 bt tieon path «0 an RR 
Holly’s Art of Saw Piling es. sik ib.cinic ik ca kiccccnenvicedis% PRES SS Rete 18mo, 
* Johnson’s (W. W.) Theoretical Mechanics. ...............c00eeees I2mo, 
Johnson’s (L. J.) Statics by Graphic and Algebraic Methods........... ,8vo, 
Jones’s Machine Design: 
Part I.—Kinematics of Machinery............... he sable es a cane 
Part I1.—Form, Strength, and Proportions a Parts..... adeapucesamhes 
Kerr’s Power and Power Transmission............. de ach ate thew enacts 
Lanza’s Applied Mechanics. ...........cccccccccccevccvcces ceecnee pees 
Leonards Machine Shops, Tools, and Methods. (Jn press.) 
MacCord’s Kinematics; or, Practical Mechanism....,....... Oe eee Ss 
Velocity Diagrams........ Pilg sare wee a sec Whenwe ss A Peng 8vo, 
Maurer’s Technical Mechanics. ..........cceeeceees Aamen ekeenle oats 
Merriman’s Text-book on the Mechanics of Materials...... bigietin oS geeckes 
* Michie’s Elements of Analytical Mechanics.............. wake e Eceiadihe 8vo, 
Reagan’s Locomotives: Simple, Compound, and Electric..... eocceces-S52M0, 
Reid’s Course in Mechanical Drawing.............cccccccccccceccces 8vo, 
Text-book of Mechanical Drawing and Elementary Machine Design. .8vo, 
Richards’s Compressed: Alt « «.o.6:6'sic ela Liisic ce bis Weve wo eae eSioead I2mo, 
Robinson’s Principles of Mechanism.............-.ee0% penis saiedowntle 8vo, 
Ryan, Norris, and Hoxie’s Electrical Machinery. WOk 2itibie Secs A, 8vo, 
Schwamb and Merrill’s Elements of Mechanism....................... 8vo, 
Sinclair’s Locomotive-engine Running and Management.............. 12mo, 
Smith’s Press-working of Metals. oo. ccc este ces doccte Uesuwebbeceeluk 8vo, 
Materials of Machines. .2 00/0 Soc c ec cc eke ees Face Vee wen Geen 0ram0; 
Spangler, Greene, and Marshall’s Elements of Steam-engineering....... 8vo, 
Thurston’s Treatise on Friction and Lost Work in Machinery and Mill 
Work....... ERTS Clow bieles aes aGisckls elec ida <eREMe Cae n'va k's vO, 
Animalasa Machine and Prime Motor, and the Laws of Energetics. 12mo, 
Warren’s Elements of Machine Construction and Drawing............. 8vo, 
Weisbach’s Kinematics and the Power of Transmission. (Herrmann— 
Klein) os ae Ae ee REE ein Ves o's’ 60 bee E Rees 8vo, 
Machinery of Tiatsiiiiealos and Governors. (Herrmann—Klein.).8vo, 
Wood’s Elements of Analytical Mechanics...... bith pete We see eae venes 
Principles of Elementary Mechanics..... ipl ne eal pieleD woe ere a ses 
Turbinegs 2264s 54 bss kh erases? x wish s ROMA MO We ewes Kemaks soe 


The World’s Columbian Exposition of tk Per PS TT eT TTT Ee Cy rT re 
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METALLURGY. 
Egleston’s Metallurgy of Silver, Gold, and Mercury: 


Vol; 3.=-Silvwets so. 3 6 sete eccccceecce eee eee ebbbeeeeseacrs 8vo, 
Wok I—Gold and Mereury.... 0. cccacescrsansesces ae ated eraieised 8vo, 
** Tles’s Lead-smeiting. (Postage 9 cents additional.) ..... Se Pees I2mo, 
Keep’s Cast Iron...... Re ee a Spe Ne ae bala SS apne 8vo, 
Kunhardt’s Practice of Ore Dressing in Europe..............-2.0-00. 8vo, 
Le Chatelier’s High-temperature Measurements. (Boudouard—Burgess.).12mo, 
Metcalf’s Steel. A Manual for Steel-users...........ccccccccccceees I2mo, 
Smith’s Materials of Machines. .........sccccceececee a euler sa oa.e a eee 
Thurston’s Materials of Engineering. “In Three Parts........... Spee 8vo, 
Part II.—Iron and Steel....... CodSia sd walbe swe eRe RCo Re eae Oe 8vo, 
Part II.—A Treatise on Brasses, Bronzes, and Other Alloys and their 
a ny eer eines gan cial a eee ag hele a aia's 8vo, 
Ulke’s Modern Electrolytic Copper Refining..... He tedeatanecesaces cats 
MINERALOGY. 
Barringer’s Description of Minerals of Commercial Value. Oblong, morocco, 
Boyd’s Resources of Southwest Virginia........... PVC EOC i cose 8vo, 
Map of Southwest Virginia, < 2665655000 8283' Des Oeex Pocket-book form, 
Brush’s Manual of Determinative Mineralogy. | A ere 8vo, 
Chester’s Catalogue of Minerals............ SELES i Lapa errr 
. 
Dictionary of the Names of Minerals. ............sccceceseceesss 8vo, 
Dana’s System of Mineralogy............cceeeeee: Large 8vo, half leather, 1 
First Appendix to Dana’s New “System of Mineralogy.”....Large 8vo, 
Text-book of Mineralogy...........ccccccececes Jacke ha escc. qs «8VOn 
Minerals and How to Study Them........... idsidh ddowewes des 12mo, 
Catalogue of American Localities of Minerals..............Large 8vo, 
Manual of Mineralogy and Petrography...... BiBid obib Sd Sade e cde SANDS 
Douglas’s Untechnical Addresses on Technical Subjects............--- I2mo, 
Eakle’s Mineral Tables...... pa S AA mee auew a dae cawe de aw as ce eens 
Egleston’s Catalogue of Minerals and Synonyms...............-e0---- 8vo, 


Hussak’s The Determination of Rock-forming Minerals. (Smith.) Small 8vo, 
Merrill’s Non-metallic Minerals: Their Occurrence and Uses.............8vo, 
* Penfield’s Notes on Determinative Mineralogy and Record of Mineral Tests. 


Svo, paper, 
Rosenbusch’s Microscopical Physiography of the Rock-making Minerals. 
CIAEINEE.) sana cseans vie NS VON Bika olen GU a at dge <6 66.000 «'a.p.0e 8vo, 


* Tillman’s Text-book of Important Minerals and Docks...............8v0, 
Williams’s Manual of EARIOIOGY 5c 5 a nck whectitatadiwecces 4necces a0 sOts 


MINING. 


Beard’s Ventilation of WIOR SS cua cae tesa date cae cecebebosececcoese I2mo, ; 


Boyd’s Resources of Southwest Virginia... ...... cc ccccc ccc cccccccces: 8vo, 

Map of Southwest Virginia... .......... 0. cece econ Pocket-book form, 
Douglas’s Untechnical Addresses on Technical Subjects. ............. I2mo, 
* Drinker’s Tunneling, Explosive Compounds, and Rock Drills. 


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Eissler’s Modern High Explosives..... PEEP POP eT TTT ee A. tay | 
Fowler's Somene: Works Anghy00s «00.05 ccedecepeccccccecsservcscess rant, 
Goodyear’s Coal-mines of the Western Coast of the United States...... 12mo, 
SCO SABRE OP UMS 5 ois 5 a SST US ose esses eon eewet~ 8vo, 
** Tles’s Lead-smelting. (Postage oc. additional.) .............2.2.- 12mo, 
Kunhardt’s Practice of Ore Dressing in Europe.............. rer 8vo, 
O’Driscoll’s Notes on the Treatment of Gold Ores....... dhe ONWaGK + Eis 8vo, 
* Walke’s Lectures on Explosives........... Shevessec sa cet dnieartas « 8vo, 
Wilson’s Cyanide Processes.-........ ike odcce ce oeeens « higacs ape Eas 

Chiorination ProceaB.....cccccsccocccccs Sadueeciebeces ces ahs MO 


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_ ‘Wilson’s Hydraulic and Placer Mining. ..........cceccscscecscceces T2mo, 
Treatise on Practical and Theoretical Mine Ventilation,....... .--I2mo, 
SANITARY SCIENCE. 
Folwell’s Sewerage. (Designing, Construction, and Maintenance.)...... 8vo, 
Water-stupply Engineeting: .. 5. bias sole ows sve oes e ase ee’ 8vo, 
Fuertes’s Water and Public Health. ............ 2.000 ccc ceeeceeeess 12mo, 
Watershiitrotom- WOUKS, 6 orcs ick Awan cae ee wee tae pee Steen I2mo, 
Gerhard’s Guide to Sanitary House-inspection. .. ................... 16mo, 
Goodrich’s Economical Disposal of Town’s Refuse............... Demy 8vo, 
Hazen’s Filtration of Public Water-supplies.....................0.--. 8vo, 
Leach’s The Inspection and Analysis of Food with Special Reference to State, 
NEPA bss ss ok & WE Suk} Oe Oe a 8vo, 
Mason’s Water-supply. (Considered Principally from a Sanitary Stand- 
most.) “SO Railton, REWHIMBN, wh re oe See ee 8vo, 
Examination of Water. (Chemical and Bacteriological.)........ I2mo, 
Merriman’s Elements of Sanitary Engineering. ....................... 8vo, 
UE et ES Lis Uinta ate i ep ik soc ee winter eas I2mo, 
Prescott and Winslow’s Elements of Water Bacteriology, with Special Reference 
So-canstary: Water Analysis, ... = 60... 1.010. winless Viasipiere.t = abe I2mo, 
* Price’s Handbook on Sanitation ............ pita bie niay Ants On a Ee I2mo, 
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